CN110769685B - Agricultural and horticultural mulch film and method for producing same - Google Patents

Agricultural and horticultural mulch film and method for producing same Download PDF

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CN110769685B
CN110769685B CN201880038444.0A CN201880038444A CN110769685B CN 110769685 B CN110769685 B CN 110769685B CN 201880038444 A CN201880038444 A CN 201880038444A CN 110769685 B CN110769685 B CN 110769685B
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ultrafine particles
tungsten oxide
composite tungsten
oxide ultrafine
agricultural
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CN110769685A (en
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常松裕史
长南武
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
    • A01G13/0268—Mats or sheets, e.g. nets or fabrics
    • A01G13/0275—Films
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
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    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Abstract

The present invention provides an agricultural and horticultural mulch film which absorbs infrared rays from sunlight to heat the ground, and when the agricultural and horticultural mulch film is used in a greenhouse or the like, the temperature of the greenhouse or the like does not rise. The present invention provides an agricultural and horticultural mulch film having an infrared light absorbing layer containing infrared light absorbing material ultrafine particles, wherein the infrared light absorbing material ultrafine particles are composite tungsten oxide ultrafine particles, and the composite tungsten oxide ultrafine particles are: the composite tungsten oxide ultrafine particles have an XRD peak intensity ratio of 0.13 or more, where 1 is an XRD peak intensity value on the (220) plane of a silicon powder standard sample (640 c, manufactured by NIST).

Description

Agricultural and horticultural mulch film and method for producing same
Technical Field
The present invention relates to an agricultural and horticultural mulch film and a method for producing the same.
Background
As a method for promoting plant growth, the following methods are known: a method of coating the surface of soil with a reflective sheet using a metal film such as aluminum, a sheet reflecting white light using a film of a white light reflective material, a sheet further coated with a reflective material on the reflective sheet, or the like. On the other hand, as a sheet for keeping the ground warm, there are generally known: synthetic resin sheets such as polyethylene and polyvinyl chloride.
However, since these reflective-coated sheets reflect all of the sunlight reaching the ground surface, the infrared light that is supplied is also reflected while promoting plant growth, and when used in a greenhouse or the like, there is a problem that the temperature of the atmosphere in the greenhouse or the like rises. In addition, a reflective sheet using a metal film such as aluminum generally has a problem of cost increase due to aluminum vapor deposition processing.
On the other hand, a synthetic resin sheet for insulating the ground generally has a high infrared transmittance, and thus the insulating effect of the ground is insufficient.
To solve these problems, patent document 1 proposes a heat-insulating sheet in which a woven fabric is formed by forming a belt-like film having infrared reflection properties and a belt-like film having infrared absorption properties as warp yarns or weft yarns, respectively, and the woven fabric covers the floor surface.
Further, the film for crop cultivation proposed in patent document 2 is obtained by dispersing a pigment such as black or blue, e.g., carbon black, in a binder and printing the dispersion on the surface of a whitened film having a total light transmittance of 3.0% or more and a diffuse reflectance of 40% or more.
In the soil covering film for agriculture and horticulture proposed in patent document 3, although the reflectance of visible light is high, tungsten oxide fine particles and composite tungsten oxide ultrafine particles are selected as the material that absorbs infrared light, and these fine particles are contained as the near-infrared light absorbing component.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 9-107815
Patent document 2: japanese laid-open patent publication No. 55-127946
Patent document 3: WO2006/100799 publication
Disclosure of Invention
Technical problem to be solved by the invention
However, according to the study of the present inventors, the heat insulating sheet of patent document 1 has a problem of high production cost because the film having infrared reflectivity is formed by aluminum vapor deposition treatment.
In addition, the film for crop cultivation of patent document 2 has a problem that the effect of heating soil is insufficient because the area of the colored coating layer is 1.0 to 60% and the film is not configured to efficiently absorb the infrared ray that provides heat.
Further, by using the agricultural and horticultural mulch film of patent document 3, it is possible to supply light necessary for plant growth to the plant side, absorb infrared rays and heat the soil, and when used in a greenhouse or the like, it is possible to avoid raising the temperature of the atmosphere in the greenhouse or the like. However, according to further studies by the present inventors, the tungsten oxide fine particles or composite tungsten oxide ultrafine particles produced by the method proposed in patent document 3 have low crystallinity, and thus the infrared absorption characteristics of the agricultural or horticultural covering film containing the fine particles are insufficient.
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an agricultural and horticultural mulch film that absorbs infrared rays from sunlight to heat the ground, and that does not cause an increase in the temperature of the inside of a greenhouse when the agricultural and horticultural mulch film is used in the greenhouse, and a method for producing the same.
Means for solving the problems
The present inventors have intensively studied to solve the above problems. As a result, they have found that the composite tungsten oxide ultrafine particles have a predetermined peak intensity ratio in an X-ray diffraction (sometimes referred to as "XRD" in the present invention) pattern. Specifically, the present inventors have found that the composite tungsten oxide ultrafine particles have an XRD peak intensity ratio of 0.13 or more, when the XRD peak intensity value of the (220) plane of the silicon powder standard sample (640 c, manufactured by NIST) is 1.
The composite tungsten oxide ultrafine particles have excellent infrared absorption characteristics because they are transparent in the visible light region and have high crystallinity. Further, a dispersion containing the composite tungsten oxide ultrafine particles having general versatility can be produced with high productivity.
Further, the present inventors have found that an infrared absorbing film containing the composite tungsten oxide ultrafine particles as an infrared absorbing component can more efficiently absorb light in the sunlight, particularly in the near infrared region, and transmit light in the visible region without using the interference effect of light, and thus have completed the present invention.
That is, the first invention for solving the above-mentioned problems is as follows:
an agricultural and horticultural covering film having an infrared light absorbing layer containing ultrafine particles of an infrared absorbing material, wherein,
the infrared absorption material ultrafine particles are composite tungsten oxide ultrafine particles,
the composite tungsten oxide ultrafine particles are as follows: the composite tungsten oxide ultrafine particles have an XRD peak intensity ratio of 0.13 or more, where 1 is an XRD peak intensity value on the (220) plane of a silicon powder standard sample (640 c, manufactured by NIST).
The second invention is as follows:
the agricultural or horticultural covering film according to the first aspect of the invention is characterized in that an infrared light absorbing layer in which the infrared absorbing material ultrafine particles are dispersed and present in a resin binder is provided on at least one surface of the agricultural or horticultural covering film.
The third invention is as follows:
the agricultural or horticultural covering film according to the first or second aspect of the present invention, wherein the infrared absorbing material ultrafine particles are present dispersedly inside the film of the agricultural or horticultural covering film.
The fourth invention is as follows:
the agricultural or horticultural covering film according to any one of the first to third aspects of the invention, wherein the composite tungsten oxide ultrafine particles have a crystallite particle size of 1nm or more and 200nm or less.
The fifth invention is as follows:
the agricultural or horticultural covering film according to any one of the first to fourth aspects of the invention, wherein the composite tungsten oxide ultrafine particles are composite tungsten oxide ultrafine particles represented by the general formula MxWyOz (wherein M is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb, W is tungsten, O is oxygen, x/y 0.001. ltoreq. x/y.ltoreq.1, and 2.0< z/y.ltoreq.3.0).
The sixth invention is as follows:
the agricultural and horticultural covering film according to any one of the first to fifth inventions, wherein the composite tungsten oxide ultrafine particles contain a hexagonal crystal structure.
The seventh invention is as follows:
the agricultural or horticultural covering film according to any one of the first to sixth aspects of the invention, wherein the content of volatile matter in the composite tungsten oxide ultrafine particles is 2.5% by mass or less.
The eighth invention is as follows:
the agricultural or horticultural covering film according to any one of the first to seventh aspects of the invention, wherein the surfaces of the composite tungsten oxide ultrafine particles are coated with an oxide containing at least one or more elements selected from Si, Ti, Zr and Al.
The ninth invention is as follows:
the agricultural and horticultural covering film according to any one of the first to eighth inventions, wherein the film is at least one or more selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, ethylene-vinyl acetate, and polyester resin.
The tenth invention is as follows:
the agricultural and horticultural covering film according to any one of the first to ninth aspects of the invention is a covering film for agricultural and horticultural use, which includes a white light reflecting layer in which a white light reflecting material is dispersed, inside the film.
The eleventh invention is as follows:
the mulching film for agriculture and horticulture according to any one of the first to ninth inventions, wherein,
the agricultural and horticultural covering film is provided on one surface thereof with: a white light reflecting layer formed by coating a white light reflecting material and an infrared light absorbing layer formed by coating ultrafine particles of an infrared absorbing material on the white light reflecting layer, or,
the agricultural and horticultural covering film has a white light reflecting layer formed by coating a white light reflecting material on one surface thereof and has an infrared light absorbing layer formed by coating ultrafine particles of an infrared absorbing material on the other surface thereof.
The twelfth invention is as follows:
the agricultural or horticultural covering film according to the tenth or eleventh aspect of the invention, wherein the white light reflecting material is selected from TiO2、ZrO2、SiO2、Al2O3、MgO、ZnO、CaCO3、BaSO4、ZnS、PbCO3At least one of them.
The thirteenth invention is as follows:
a method for producing an agricultural and horticultural mulch film having an infrared light absorbing layer containing ultrafine particles of an infrared absorbing material,
the infrared absorbing material ultrafine particles are composite tungsten oxide ultrafine particles,
firing is performed to produce the composite tungsten oxide particles so that when the XRD peak intensity value of the (220) plane of a silicon powder standard sample (NIST, 640c) is 1, the ratio of the XRD peak top intensity of the composite tungsten oxide particles becomes 0.13 or more,
the composite tungsten oxide particles thus produced are added to the infrared light absorbing layer while maintaining the ratio of the XRD peak intensity at 0.13 or more.
Effects of the invention
Since the agricultural and horticultural covering film of the present invention can efficiently absorb infrared rays from sunlight, the agricultural and horticultural covering film is used for a ground surface for growing plants or the like, so that the temperature of the covered ground surface is increased and the soil is warmed. On the other hand, when the soil covering film for agriculture and horticulture is used in a greenhouse or the like, there is an effect of preventing the temperature of the atmosphere in the greenhouse or the like from rising.
Drawings
FIG. 1 is a conceptual view of a high-frequency plasma reactor used in the present invention.
FIG. 2 shows an X-ray diffraction pattern of ultrafine particles of example 1.
Detailed Description
The following description will discuss embodiments of the present invention in the order of [ a ] composite tungsten oxide ultrafine particles, [ b ] a method for synthesizing composite tungsten oxide ultrafine particles, [ c ] a method for drying volatile components of composite tungsten oxide ultrafine particles, [ d ] a composite tungsten oxide ultrafine particle dispersion, and [ e ] an agricultural or horticultural covering film.
[a] Composite tungsten oxide ultrafine particle
The soil-covering film for agriculture and horticulture of the present invention is a film provided with a white light reflecting layer containing a white light reflecting material and an infrared light absorbing layer containing composite tungsten oxide ultrafine particles as infrared absorbing material ultrafine particles, and has characteristics of high diffuse reflectance of light in the visible light region and high light absorbance in the infrared region. First, composite tungsten oxide ultrafine particles as infrared absorbing material ultrafine particles will be described.
The composite tungsten oxide ultrafine particles of the present invention have near-infrared absorption characteristics, and when the XRD peak intensity of the (220) plane of a silicon powder standard sample (640 c, manufactured by NIST) is 1, the ratio of the XRD peak top intensity of the composite tungsten oxide ultrafine particles is 0.13 or more.
The composite tungsten oxide ultrafine particles of the present invention will be described below in the order of (1) the ratio of XRD peak intensities, (2) the composition, (3) the crystal structure, (4) the BET specific surface area, (5) the volatile component, and (6).
(1) Ratio of XRD Peak intensity
In the XRD peak intensity measurement of the composite tungsten oxide ultrafine particles, a powder X-ray diffraction method was used. In this case, in order to obtain objective quantitative measurement results among the samples of the composite tungsten oxide ultrafine particles, a standard sample was defined, the peak intensity of the standard sample was measured, and the ratio of the XRD peak top intensity of the ultrafine particles to the peak intensity of the standard sample was defined as the XRD peak top intensity of each ultrafine particle sample.
Here, the standard sample is a silicon powder standard sample (manufactured by NIST, 640c) that is common in the industry, and the (220) plane in the silicon powder standard sample is set as a reference, which is not overlapped with the XRD peak of the composite tungsten oxide ultrafine particle.
Further, in order to ensure objective quantitativity, other measurement conditions are also generally constant.
Specifically, an ultrafine particle sample was filled in a sample holder having a depth of 1.0mm according to a known procedure in X-ray diffraction measurement. Specifically, in order to avoid the occurrence of a preferential orientation (crystal alignment) in the ultrafine particle sample, it is preferable to fill the sample randomly and slowly, and to fill the sample densely while minimizing unevenness.
The X-ray source was measured by a powder X-ray diffraction method using an X-ray tube ball made of Cu as a target material of an anode, and having an output of 45kV/40mA, using a theta-2 theta in a step-and-scan mode (step size: 0.0165 DEG (2 theta), count time: 0.022 msec/step).
In this case, since the XRD peak intensity changes depending on the use time of the X-ray tube, the use time of the X-ray tube is preferably substantially the same between samples. In order to ensure objective quantification, the maximum difference between samples of the X-ray tube bulb service time must be less than 20-1 of the predicted life of the X-ray tube bulb. More preferred measurement methods include the following methods: and a method of measuring a silicon powder standard sample and calculating the ratio of the XRD peak intensities for each measurement of the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles. The present invention uses this measurement method. Since the life of an X-ray tube bulb of a commercially available X-ray apparatus is predicted to be substantially several thousand hours or more and the measurement time of each sample is several hours or less, the influence of the X-ray tube bulb use time on the ratio of the XRD peak top intensities can be reduced to be negligible by carrying out the above-described preferable measurement method.
In order to keep the temperature of the X-ray tube constant, the temperature of the cooling water for the X-ray tube is preferably kept constant.
The X-ray diffraction pattern of the composite tungsten oxide ultrafine particles is an X-ray diffraction pattern of a plurality of composite tungsten oxide ultrafine particles constituting a powder sample of the composite tungsten oxide. In order to obtain a composite tungsten oxide ultrafine particle dispersion, the following X-ray diffraction pattern of the composite tungsten oxide ultrafine particles is set, which are crushed, pulverized, or dispersed. The X-ray diffraction pattern of the composite tungsten oxide ultrafine particles of the present invention and the composite tungsten oxide ultrafine particles contained in the dispersion thereof is also retained in the X-ray diffraction pattern of the composite tungsten oxide ultrafine particle dispersion of the present invention.
The XRD peak top intensity is the peak intensity at 2 θ where the peak count is the highest in the X-ray diffraction pattern. In addition, in the Cs composite tungsten oxide and the Rb composite tungsten oxide of hexagonal crystal, the peak count 2 θ in the X-ray diffraction pattern appears in the range of 25 ° to 31 °.
The XRD peak top intensity of the composite tungsten oxide ultrafine particle has a close relationship with the crystallinity of the ultrafine particle, and further has a close relationship with the free electron density of the ultrafine particle. The present inventors have found that the XRD peak top intensity greatly affects the near-infrared absorption characteristics of the composite tungsten oxide ultrafine particles. Specifically, it was found that desired near infrared absorption characteristics can be obtained by securing the free electron density of the ultrafine particles by setting the ratio of the XRD peak top intensities to 0.13 or more. The ratio of the XRD peak intensity is preferably 0.13 or more, and more preferably 0.7 or less.
The XRD peak top intensity of the composite tungsten oxide ultrafine particles is also explained from a different viewpoint.
The ratio of the XRD peak intensity of the composite tungsten oxide ultrafine particles is 0.13 or more, and it is shown that composite tungsten oxide ultrafine particles having excellent crystallinity and containing substantially no heterogeneous phase can be obtained. That is, it is considered that the obtained composite tungsten oxide ultrafine particles are not amorphized (noncrystalline). As a result, the composite tungsten oxide ultrafine particles containing substantially no hetero-phase are dispersed in a liquid medium such as an organic solvent that transmits visible light and a solid medium such as a resin that transmits visible light, whereby near-infrared absorption characteristics can be sufficiently obtained.
In the present invention, the "heterogeneous phase" refers to a phase of a compound other than the composite tungsten oxide. Further, the crystal structure and crystallite diameter of the composite tungsten oxide ultrafine particles can be determined by analyzing the X-ray diffraction pattern obtained by measuring the XRD peak intensity.
(2) Composition of
The composite tungsten oxide ultrafine particles of the present invention are preferably composite tungsten oxide ultrafine particles represented by the general formula MxWyOz (wherein M is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb, W is tungsten, O is oxygen, x/y is 0.001. ltoreq. x/y.ltoreq.1, and 2.0< z/y. ltoreq.3. 0).
The composite tungsten oxide ultrafine particles represented by the general formula MxWyOz are described.
The M element, x, y, z and the crystal structure thereof in the general formula MxWyOz have close relation with the free electron density of the composite tungsten oxide ultrafine particles, and the near infrared ray absorption characteristic is greatly influenced.
In general, because of tungsten trioxide (WO)3) Does not have effective free electrons, and thus has low near infrared absorption characteristics.
The inventors herein have found that a composite tungsten oxide is produced by adding an M element (wherein the M element is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb) to the tungsten oxide, free electrons are generated in the composite tungsten oxide, and the composite tungsten oxide exhibits absorption characteristics derived from the free electrons in the near-infrared region, and is an effective material as a near-infrared absorbing material having a wavelength of about 1000nm, the composite tungsten oxide is chemically stable, and is an effective material as a near-infrared absorbing material having excellent weather resistance. The M element is preferably Cs, Rb, K, Tl, Ba, Cu, Al, Mn, In, and when the M element is Cs or Rb, the composite tungsten oxide tends to have a hexagonal crystal structure. As a result, it was found that the transparent conductive film is particularly preferable from the viewpoint of transmitting visible light and absorbing near infrared rays for the following reasons.
Here, the present inventors will explain the knowledge of the x value indicating the addition amount of the M element.
When the x/y value is 0.001 or more, a sufficient amount of free electrons can be generated, and the desired near infrared absorption characteristics can be obtained. Further, as the amount of the element M added increases, the amount of free electrons supplied increases, and the near-infrared absorption characteristics are also improved, but when the x/y value is about 1, the effect is saturated. It is preferable that the x/y value is 1 or less because the formation of an impurity phase in the composite tungsten ultrafine particles can be avoided.
Next, the present inventors will explain the findings on the z value indicating the control of the oxygen amount.
In the ultrafine composite tungsten oxide particles represented by the general formula MxWyOz, the z/y value is preferably 2.0<z/y.ltoreq.3.0, more preferably 2.2. ltoreq. z/y.ltoreq.3.0, particularly preferably 2.6. ltoreq. z/y.ltoreq.3.0, most preferably 2.7. ltoreq. z/y.ltoreq.3.0. The reason is that, if the z/y value is 2.0 or more, the occurrence of WO other than the target WO in the composite tungsten oxide can be avoided2A crystalline phase and chemical stability as a material can be obtained, and thus can be suitably used as an effective infrared absorbing material. On the other hand, when the z/y value is 3.0 or less, a necessary amount of free electrons are generated in the tungsten oxide, and the infrared absorbing material has high efficiency.
(3) Crystal structure
The composite tungsten oxide ultrafine particles may have a tetragonal or cubic tungsten bronze structure in addition to a hexagonal structure, and are effective as a near-infrared absorbing material regardless of the structure. However, the absorption sites in the near-infrared region tend to change depending on the crystal structure of the composite tungsten oxide ultrafine particles. That is, the absorption position in the near infrared region tends to shift further to the longer wavelength side in the case of tetragonal crystals than in the case of cubic crystals, and tends to shift further to the longer wavelength side in the case of hexagonal crystals than in the case of tetragonal crystals. In addition, as the absorption position varies, the absorption in the visible light region is due to the least hexagonal crystals followed by the tetragonal crystals, and the largest is due to the cubic crystals.
According to the above findings, hexagonal tungsten bronze is preferably used for applications in which light in the visible light region is further transmitted and light in the infrared region is further absorbed. When the composite tungsten oxide ultrafine particles have a hexagonal crystal structure, the visible light region transmission of the fine particles is improved, and the near-infrared region absorption is improved.
That is, the composite tungsten oxide has a ratio of XRD peak top intensities satisfying the above-mentioned predetermined value, and exhibits excellent optical properties even when it is hexagonal tungsten bronze. Further, when the composite tungsten oxide ultrafine particles have a crystal structure of orthorhombic crystals or have a phase with WO called Magnelli (Magneli)2.72The same monoclinic crystal structure is excellent in infrared absorption and can be effectively used as a near-infrared absorbing material.
From the above findings, it is found that when the composite tungsten oxide ultrafine particles having a hexagonal crystal structure have a uniform crystal structure, the amount of the element M added is preferably 0.2 to 0.5 in terms of x/y, and more preferably 0.29. ltoreq. x/y. ltoreq.0.39. Theoretically, when z/y is 3, it is considered that the additive M element is arranged in all the voids of the hexagonal shape since the value of x/y becomes 0.33. Typical examples include: cs0.33WO3、Cs0.03Rb0.30WO3、Rb0.33WO3、K0.33WO3、Ba0.33WO3And the like.
In the composite tungsten oxide ultrafine particles of the present invention, a single crystal having an amorphous phase volume ratio of 50% or less is preferable.
When the composite tungsten oxide ultrafine particles are a single crystal in which the volume ratio of the amorphous phase is 50% or less, the crystallite particle size can be set to 200nm or less while maintaining the XRD peak intensity. By setting the crystallite diameter of the composite tungsten oxide ultrafine particles to 200nm or less, the dispersion particle diameter thereof can be set to 10nm or more and 200nm or less as a preferable range from the viewpoint of the near-infrared ray absorption characteristics and the visible light transmission characteristics.
On the other hand, in the composite tungsten oxide ultrafine particles, the dispersed particle diameter is 1nm or more and 200nm or less, but when the amorphous phase is present in a proportion of more than 50% by volume or when the amorphous phase is polycrystalline, the ratio of the XRD peak top intensity of the composite tungsten oxide ultrafine particles becomes less than 0.13, and as a result, the near-infrared ray absorption characteristics are insufficient, and the near-infrared ray absorption characteristics are not sufficiently expressed.
On the other hand, from the viewpoint of near-infrared absorption characteristics, the crystallite diameter of the composite tungsten oxide fine particles is preferably 10nm or more. Further, the crystallite diameter of the composite tungsten oxide ultrafine particles is more preferably 200nm or less and 10nm or more. The reason is that when the crystallite diameter is in the range of 200nm or less and 10nm or more, the ratio of the XRD peak top intensities exceeds 0.13, and more excellent near-infrared absorption characteristics can be exhibited.
The X-ray diffraction pattern of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion liquid after the crushing, grinding or dispersion described below is also retained by the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles obtained by removing volatile components from the composite tungsten oxide ultrafine particle dispersion liquid of the present invention and the X-ray diffraction pattern of the composite tungsten oxide ultrafine particles contained in the dispersion liquid obtained from the dispersion liquid.
As a result, the effects of the present invention can be exhibited when the crystal state of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion liquid and the composite tungsten oxide ultrafine particle dispersion obtained from the dispersion liquid is the crystal state of the composite tungsten oxide ultrafine particles usable in the present invention, such as the XRD pattern, the XRD peak intensity, and the crystallite particle diameter.
The composite tungsten oxide ultrafine particles are single crystals and can be confirmed as follows: in an electron microscope image such as a transmission electron microscope, crystal grain boundaries are not observed in the respective fine particles, and only the same lattice grains are observed. Further, the volume ratio of the amorphous phase in the composite tungsten oxide ultrafine particles of 50% or less can be confirmed by: also in the transmission electron microscope image, the same lattice pattern was observed throughout the particle, and substantially no unclear portion of the lattice pattern was observed. Since the amorphous phase is present in many cases in the outer periphery of the particle, the volume fraction of the amorphous phase can be calculated in many cases by focusing attention on the outer periphery of the particle. For example, in the case where an amorphous phase having an unclear lattice grain is present in a layer form at the outer periphery of the particle in the spherical composite tungsten oxide ultrafine particle, the volume ratio of the amorphous phase in the composite tungsten oxide ultrafine particle is 50% or less when the thickness is 10% or less of the particle diameter. The composite tungsten oxide ultrafine particles are substantially single crystals.
On the other hand, when the composite tungsten oxide ultrafine particles are dispersed in a coating film constituting a dispersion of composite tungsten oxide ultrafine particles, a film obtained by curing a resin of the coating film (which may be referred to as a "cured film" in the present invention and corresponds to the "infrared light absorbing layer" in the present invention), a resin, or the like by performing a predetermined operation on the coating film, if the difference obtained by subtracting the crystallite particle diameter from the average particle diameter of the dispersed composite tungsten oxide ultrafine particles is 20% or less, it can be said that the composite tungsten oxide ultrafine particles are a single crystal having a volume proportion of an amorphous phase of 50% or less.
Here, the average particle diameter of the composite tungsten oxide ultrafine particles can be determined by: from the transmission electron microscope image of the composite tungsten oxide ultrafine particle dispersion, the particle diameters of 100 composite tungsten oxide ultrafine particles were measured using an image processing apparatus, and the average value thereof was calculated. The synthesis step, the pulverization step, and the dispersion step of the composite tungsten oxide ultrafine particles may be appropriately adjusted depending on the production equipment so that the difference between the average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the composite tungsten oxide ultrafine particle dispersion and the crystallite particle diameter is 20% or less.
(4) BET specific surface area
The BET specific surface area of the composite tungsten oxide ultrafine particles is closely related to the particle size distribution of the ultrafine particles, and the productivity of a near-infrared-ray-absorbing dispersion using the ultrafine particles as a raw material, the near-infrared-ray absorption characteristics of the ultrafine particles themselves, and the light resistance to suppress light coloring are greatly affected.
The smaller BET specific surface area of the ultrafine particles indicates that the crystallite size of the ultrafine particles is larger. Therefore, when the BET specific surface area of the ultrafine particles is equal to or greater than a predetermined value, the ultrafine particles have transparency in the visible light region, and when the near infrared ray absorption dispersion liquid capable of suppressing the blue haze (blue haze) phenomenon is produced, the ultrafine particles are pulverized and micronized for a long time without using a medium-stirring mill, and the productivity of the near infrared ray absorption dispersion liquid can be improved.
On the other hand, the BET specific surface area of the ultrafine particles is not more than a predetermined value, for example, 200m2The BET particle diameter of 2nm or more when the particle shape is assumed to be spherical means that ultrafine particles having a crystallite particle diameter of less than 1nm, which do not contribute to the near infrared absorption characteristics, are substantially absent. Therefore, when the BET specific surface area of the ultrafine particles is equal to or less than a predetermined value, the near infrared absorption characteristics and light resistance of the ultrafine particles can be ensured.
In particular, the BET specific surface area in the ultrafine particles is 200m2When the ratio of the XRD peak top intensities is equal to or greater than a predetermined value,/g or less, ultrafine particles having a crystallite particle diameter of less than 1nm, which do not contribute to the near-infrared absorption characteristics, are substantially absent, and ultrafine particles having good crystallinity are present, and therefore it is considered that the near-infrared absorption characteristics and light resistance of the ultrafine particles can be ensured.
In the measurement of the BET specific surface area of the composite tungsten oxide ultrafine particles, nitrogen, argon, krypton, xenon, or the like is used as a gas for adsorption. In particular, the test sample was a powder as the composite tungsten oxide ultrafine particles of the present invention, and the specific surface area reached 0.1m2At a concentration of at least one of the components,/g, it is preferable to use a nitrogen gas which is easy to handle and low in cost. The BET specific surface area of the composite tungsten oxide ultrafine particles is preferably 30.0m2120.0m and more/g2A ratio of 30.0m or less per gram2More than 90.0 m/g2A specific ratio of 35.0m to less/g270.0 m/g or more2The ratio of the carbon atoms to the carbon atoms is less than g. The BET specific surface area of the composite tungsten oxide ultrafine particles is preferably the value described above before and after the pulverization and dispersion in the case of obtaining a composite tungsten oxide ultrafine particle dispersion.
(5) Volatile component
The composite tungsten oxide ultrafine particles may contain a component that volatilizes by heating (in the present invention, the component may be referred to as a "volatile component"). The volatile component is a component adsorbed during the synthesis step when the composite tungsten oxide ultrafine particles are exposed to a storage atmosphere or an atmosphere. Here, as specific examples of the volatile component, there are a case where water is present and a case where a solvent of a dispersion liquid described below is present, and for example, there is a component that volatilizes from the composite tungsten oxide ultrafine particles by heating at 150 ℃.
The volatile component and the content thereof in the composite tungsten oxide ultrafine particles are related to the amount of water adsorbed when the ultrafine particles are exposed to the atmosphere or the like and the residual amount of solvent in the drying step of the ultrafine particles. Further, the volatile component and the content thereof may greatly affect the dispersibility of the ultrafine particles when dispersed in a resin or the like.
For example, the compatibility of the resin used in the near-infrared absorbing dispersion described below with the volatile component adsorbed on the ultrafine particles may be poor, and when the content of the volatile component in the ultrafine particles is large, the haze (deterioration in transparency) may be caused in the near-infrared absorbing dispersion produced. When the near-infrared-ray-absorbing dispersion thus produced is placed outdoors for a long period of time and exposed to sunlight or wind and rain, the composite tungsten oxide ultrafine particles may be detached from the near-infrared-ray-absorbing dispersion or the film may be peeled off. That is, the deterioration of the compatibility of the ultrafine particles with the resin causes the deterioration of the near-infrared-absorbing dispersion to be produced. That is, it means that the composite tungsten oxide ultrafine particles containing a large amount of volatile components may be well dispersed depending on compatibility with a dispersion medium used in a dispersion system. Therefore, if the content of volatile components in the composite tungsten oxide ultrafine particles of the present invention is a predetermined amount or less, the present invention can exhibit wide versatility.
According to the examination by the present inventors, it has been found that when the content of volatile components in the composite tungsten oxide ultrafine particles is 2.5% by mass or less, the ultrafine particles are dispersed in a dispersion medium used in most dispersion systems, and the composite tungsten oxide ultrafine particles have general utility.
On the other hand, it is found that the lower limit of the content of the volatile component is not particularly limited.
As a result, when the ultrafine particles having a volatile content of 2.5 mass% or less are not excessively secondarily aggregated, the ultrafine particles can be dispersed in a resin or the like by a method of uniformly mixing (including melt mixing) the ultrafine particles with a Mixer such as a tumbler, Nauta Mixer (Nauta Mixer), Henschel Mixer (Henschel Mixer), high-speed Mixer, planetary Mixer, or a Mixer such as a Banbury Mixer (Banbury Mixer), kneader, roll, uniaxial extruder, or biaxial extruder.
The content of volatile components in the composite tungsten oxide ultrafine particles can be measured by thermal analysis. Specifically, the sample of the composite tungsten oxide ultrafine particles may be kept at a temperature lower than the thermal decomposition temperature of the composite tungsten oxide ultrafine particles and higher than the temperature at which volatile components volatilize, and the weight loss may be measured. When volatile components are specified, gas mass analysis may be used in combination.
(6) Conclusion
The XRD peak top intensity value and BET specific surface area of the composite tungsten oxide ultrafine particles described above in detail can be controlled by using predetermined production conditions. Specifically, in the thermal plasma method, the solid-phase reaction method, or the like, the temperature (firing temperature) for producing the ultrafine particles, the production time (firing time), the production atmosphere (firing atmosphere), the form of the precursor raw material, the annealing treatment after production, the doping of the impurity element, or the like can be controlled by appropriately setting the production conditions. On the other hand, the content of volatile components in the composite tungsten oxide ultrafine particles can be controlled by appropriately setting the production conditions such as the method and atmosphere for storing the ultrafine particles, the temperature for drying the ultrafine particle dispersion, the drying time, and the drying method. The content of volatile components in the composite tungsten oxide ultrafine particles is not dependent on the crystal structure of the composite tungsten oxide ultrafine particles, the thermal plasma method described below, the solid-phase reaction, or other synthesis methods.
[b] Synthesis method of composite tungsten oxide superfine particles
The method for synthesizing the composite tungsten oxide ultrafine particles of the present invention will be described.
Examples of the method for synthesizing the composite tungsten oxide ultrafine particles of the present invention include: a thermal plasma method in which a tungsten compound starting material is put into thermal plasma, and a solid-phase reaction method in which a tungsten compound starting material is heat-treated in a reducing gas atmosphere. The composite tungsten oxide ultrafine particles synthesized by the thermal plasma method or the solid phase reaction method are subjected to dispersion treatment or pulverization and dispersion treatment.
The following description will be made in accordance with the order of (1) thermal plasma method, (2) solid-phase reaction method, and (3) synthesized composite tungsten oxide ultrafine particles.
(1) Thermal plasma method
The thermal plasma method is described in the order of (i) the raw material used in the thermal plasma method, (ii) the thermal plasma method and the conditions thereof.
(i) Raw material for thermal plasma method
When the composite tungsten oxide ultrafine particles of the present invention are synthesized by a thermal plasma method, a mixed powder of a tungsten compound and an M element compound can be used as a raw material.
The tungsten compound is preferably selected from tungstic acid (H)2WO4) And one or more of ammonium tungstate, tungsten hexachloride, and tungsten hydrate obtained by adding water to tungsten hexachloride dissolved in alcohol, hydrolyzing the mixture, and then evaporating the solvent.
Further, as the M element compound, one or more selected from oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates of the M element are preferably used.
The tungsten compound and the aqueous solution containing the M element compound are wet-mixed so that the ratio of M element to W element is MxWyOz (where M is the M element, W is tungsten, O is oxygen, 0.001. ltoreq. x/y. ltoreq.1.0, and 2.0. ltoreq. z/y. ltoreq.3.0). Then, the obtained mixed solution is dried to obtain a mixed powder of the M element compound and the tungsten compound, which can be used as a raw material for the thermal plasma method.
In addition, a composite tungsten oxide obtained by firing the mixed powder in the first stage under an atmosphere of an inert gas alone or a mixed gas of an inert gas and a reducing gas is used as a raw material for the thermal plasma method. Further, a composite tungsten oxide obtained by the following two-stage firing may be used as a raw material for the thermal plasma method: the first step is firing in a mixed gas atmosphere of an inert gas and a reducing gas, and the fired product of the first step is fired in a second step in an inert gas atmosphere.
(ii) Thermal plasma method and conditions therefor
As the thermal plasma used in the present invention, for example: any one of dc arc plasma, high-frequency plasma, microwave plasma, and low-frequency ac plasma, or a substance in which these plasmas are superimposed, or plasma generated by an electrical method in which a magnetic field is applied to dc plasma, plasma generated by irradiation of high-output laser light, and plasma generated by a high-output electron beam or ion beam. In particular, regardless of the thermal plasma used, the thermal plasma has a high temperature portion of 10000 to 15000K, and particularly preferably a plasma in which the generation time of ultrafine particles can be controlled.
The raw material supplied to the thermal plasma having the high temperature portion is instantaneously evaporated in the high temperature portion. The evaporated raw material is condensed in the process of reaching the plasma tail flame portion, and rapidly solidified outside the plasma flame to form ultrafine composite tungsten oxide particles.
As an example when a high-frequency plasma reaction apparatus is used, a synthesis method will be described with reference to fig. 1.
First, the reaction system including the reaction vessel 6 and the water-cooled quartz double tube was evacuated to about 0.1Pa (about 0.001Torr) by a vacuum evacuation apparatus. After the reaction system was evacuated, the reaction system was filled with argon gas to form an argon gas flow system at 1 atmosphere.
Then, the user can use the device to perform the operation,introducing a gas selected from argon, a mixed gas of argon and helium (Ar-He mixed gas), or a mixed gas of argon and nitrogen (Ar-N mixed gas) into a reaction vessel at a flow rate of 30-45L/min2Mixed gas) as a plasma gas. On the other hand, an Ar-He mixed gas is introduced at a flow rate of 60 to 70L/min as a sheath gas flowing immediately outside the plasma region.
Then, an alternating current is applied to the high-frequency coil 2, and thermal plasma is generated by a high-frequency electromagnetic field (frequency 4 MHZ). In this case, the high-frequency power is set to 30 to 40 kW.
Further, the mixed powder of the M element compound and the tungsten compound or the composite tungsten oxide obtained by the above synthesis method is introduced into the thermal plasma at a supply rate of 25 to 50g/min using 6 to 98L/min of argon gas supplied from a gas supply device as a carrier gas by the raw material powder supply nozzle 5, and reacted for a predetermined time. After the reaction, the produced composite tungsten oxide ultrafine particles are collected because they are deposited on the filter 8.
The carrier gas flow rate and the raw material supply rate greatly affect the time for producing ultrafine particles. Here, it is preferable that the carrier gas flow rate is set to 6L/min to 9L/min, and the raw material supply rate is set to 25 to 50 g/min.
Preferably, the plasma gas flow rate is set to 30L/min to 45L/min, and the sheath flow rate is set to 60L/min to 70L/min. The plasma gas has a function of maintaining a thermal plasma region having a high temperature portion of 10000 to 15000K, and the sheath flow gas has a function of cooling an inner wall surface of the quartz torch tube in the reaction container to prevent melting of the quartz torch tube. Meanwhile, since the plasma gas and the sheath gas affect the shape of the plasma region, the flow rates of these gases become important parameters for controlling the shape of the plasma region. Since the shape of the plasma region extends in the gas flow direction as the flow rates of the plasma gas and the sheath gas are higher, and the temperature gradient of the plasma tail flame portion is more moderate, the longer the time for producing the produced ultrafine particles, the ultrafine particles having good crystallinity can be produced. Thus, the ratio of the XRD peak intensity of the ultrafine composite tungsten oxide particles of the present invention can be set to a desired value. On the other hand, as the flow rates of the plasma gas and the sheath gas are lower, the shape of the plasma region is more constricted in the gas flow direction, and the temperature gradient of the plasma tail flame portion is steeper. Thus, the ratio of the XRD peak top intensities of the ultrafine composite tungsten oxide particles of the present invention can be set to a predetermined value.
When the crystallite diameter of the composite tungsten oxide synthesized by the thermal plasma method exceeds 200nm, or when the dispersed diameter of the composite tungsten oxide in the composite tungsten oxide ultrafine particle dispersion liquid made of the composite tungsten oxide synthesized by the thermal plasma method exceeds 200nm, the following pulverization/dispersion treatment can be performed. When the composite tungsten oxide is synthesized by the thermal plasma method, the difference between the average particle diameter and the crystallite particle diameter of the composite tungsten oxide ultrafine particles of the composite tungsten oxide ultrafine particle dispersion of the coating film of the composite tungsten oxide ultrafine particle dispersion is set to 20% or less by appropriately selecting the plasma conditions and the subsequent conditions of pulverization and dispersion treatment so that the ratio of the XRD peak intensity is 0.13 or more, whereby the effect of the present invention can be exhibited.
(2) Solid phase reaction method
The solid-phase reaction method will be described in the order of (i) raw materials used in the solid-phase reaction method, (ii) firing in the solid-phase reaction method, and conditions thereof.
(i) Raw materials for solid phase reaction
When the composite tungsten oxide ultrafine particles of the present invention are synthesized by a solid-phase reaction method, a tungsten compound and an M element compound are used as raw materials.
The tungsten compound is preferably selected from tungstic acid (H)2WO4) And one or more of ammonium tungstate, tungsten hexachloride, and tungsten hydrate obtained by adding water to tungsten hexachloride dissolved in alcohol, hydrolyzing the mixture, and then evaporating the solvent.
In a more preferred embodiment, the M element compound used for producing the raw material of the composite tungsten oxide ultrafine particles represented by the general formula MxWyOz (where M is one or more elements selected from Cs, Rb, K, Tl and Ba, 0.001. ltoreq. x/y. ltoreq.1, and 2.0< z/y. ltoreq.3.0) is preferably one or more elements selected from oxides, hydroxides, nitrates, sulfates, chlorides and carbonates of the M element.
Further, a compound containing one or more impurity elements selected from Si, Al, and Zr (also referred to as "impurity element compound" in the present invention) may be contained as a raw material. The impurity element compound does not react with the composite tungsten compound in the subsequent firing step, and has an effect of suppressing crystal growth of the composite tungsten oxide and preventing coarsening of the crystal. The impurity element-containing compound is preferably at least one selected from the group consisting of an oxide, a hydroxide, a nitrate, a sulfate, a chloride, and a carbonate, and particularly preferably colloidal silica and colloidal alumina having a particle size of 500nm or less.
The tungsten compound and the aqueous solution containing the M element compound are wet-mixed so that the ratio of M element to W element is MxWyOz (wherein M is the M element, W is tungsten, O is oxygen, 0.001. ltoreq. x/y. ltoreq.1.0, 2.0. ltoreq. z/y. ltoreq.3.0). When the impurity element compound is contained as a raw material, wet mixing is performed so that the impurity element compound is 0.5 mass% or less. Then, the obtained mixed solution is dried to obtain a mixed powder of the M element compound and the tungsten compound or a mixed powder of the M element compound containing the impurity element compound and the tungsten compound.
(ii) Firing in solid-phase reaction method and conditions therefor
The mixed powder of the M element compound and the tungsten compound produced by the wet mixing or the mixed powder of the M element compound containing the impurity element compound and the tungsten compound is fired in 1 stage under an inert gas alone or a mixed gas atmosphere of an inert gas and a reducing gas. In this case, the firing temperature is preferably set to a temperature close to the temperature at which the composite tungsten oxide ultrafine particles start to crystallize, and specifically, the firing temperature is preferably in a temperature range of 1000 ℃ or less, more preferably 800 ℃ or less, and particularly preferably 800 ℃ or less and 500 ℃ or more. By controlling the firing temperature, the ratio of the XRD peak top intensities of the composite tungsten oxide ultrafine particles of the present invention can be set to a predetermined value.
In particular, in the synthesis of the composite tungsten oxide ultrafine particles, tungsten trioxide may be used instead of the tungsten compound.
(3) Synthesized composite tungsten oxide ultrafine particles
When the following composite tungsten oxide ultrafine particle dispersion is prepared using composite tungsten oxide ultrafine particles obtained by a synthesis method using a thermal plasma method or a solid-phase reaction method, if the dispersed particle diameter of the ultrafine particles contained in the dispersion exceeds 200nm, the composite tungsten oxide ultrafine particle dispersion may be subjected to a pulverization and dispersion treatment in the following step of producing the composite tungsten oxide ultrafine particle dispersion. Then, if the ratio of the XRD peak intensity of the composite tungsten oxide ultrafine particles obtained by the pulverization and dispersion treatment can achieve the range of the present invention, the composite tungsten oxide ultrafine particle dispersion obtained from the composite tungsten oxide ultrafine particles or the dispersion liquid thereof of the present invention can achieve excellent near-infrared absorption characteristics.
[c] Volatile component of composite tungsten oxide ultrafine particles and drying treatment method thereof
As described above, the composite tungsten oxide ultrafine particles of the present invention may contain a volatile component, and the content of the volatile component is preferably 2.5 mass% or less. However, when the content of the volatile component exceeds 2.5% by mass due to exposure of the composite tungsten oxide ultrafine particles to the air or the like, the content of the volatile component can be reduced by drying.
Specifically, the composite tungsten oxide ultrafine particles of the present invention can be produced by the following steps: a step (pulverization/dispersion treatment step) of pulverizing and dispersing the composite tungsten oxide synthesized by the above method to form fine particles and producing a composite tungsten oxide ultrafine particle dispersion; and a step (drying step) of drying the produced composite tungsten oxide ultrafine particle dispersion to remove the solvent.
The pulverizing and dispersing step is described in detail in the following item of "[ d ] composite tungsten oxide ultrafine particle dispersion liquid", and therefore the drying step is described here.
The drying step is a step of drying the composite tungsten oxide ultrafine particle dispersion obtained in the pulverizing and dispersing step described below to remove volatile components in the dispersion, thereby obtaining the composite tungsten oxide ultrafine particles of the present invention.
As the drying apparatus, from the viewpoint of enabling heating and/or pressure reduction and facilitating mixing and collection of the ultrafine particles, it is preferable that: an atmospheric dryer, a universal mixer, a belt mixer, a vacuum flow dryer, a vibrating flow dryer, a freeze dryer, a conical screw mixing dryer (RIBOCONE), a rotary kiln, a spray dryer, a PALCON dryer, etc., but not limited thereto.
Hereinafter, as examples thereof, (1) drying treatment by an air dryer, (2) drying treatment by a vacuum fluidized dryer, and (3) drying treatment by a spray dryer will be described. Hereinafter, the respective drying processes will be described in order.
(1) Drying treatment with an atmospheric dryer
A method of removing volatile components from a composite tungsten oxide ultrafine particle dispersion obtained by the following method, by drying the dispersion in an air dryer. In this case, the drying treatment is preferably performed at a temperature higher than the temperature at which the volatile component volatilizes from the composite tungsten oxide ultrafine particles and at which the element M does not escape, and is preferably 150 ℃ or lower.
The ultrafine composite tungsten oxide particles produced by the drying treatment in the air dryer become weak secondary aggregates. In this state, although the composite tungsten oxide ultrafine particles can be dispersed in a resin or the like, it is also a preferable example that the ultrafine particles are crushed by a crusher or the like for easier dispersion.
(2) Drying treatment with vacuum flow dryer
A method for removing volatile components from a composite tungsten oxide ultrafine particle dispersion by drying treatment using a vacuum fluidized dryer. Since the vacuum fluidized dryer simultaneously performs the drying and crushing processes in a reduced pressure atmosphere, aggregates which are present in the dried product in the above-described atmospheric dryer are not formed, except for a high drying speed. Since the drying is performed in a reduced pressure atmosphere, volatile components can be removed even at a relatively low temperature, and the amount of residual volatile components can be reduced without limitation.
The drying treatment is preferably carried out at a temperature at which the element M does not detach from the composite tungsten oxide ultrafine particles, and is preferably higher than a temperature at which the volatile component volatilizes, and is preferably 150 ℃.
(3) Drying treatment with a spray dryer
A method for removing volatile components from a composite tungsten oxide ultrafine particle dispersion by drying the composite tungsten oxide ultrafine particle dispersion with a spray dryer. When volatile components are removed in the drying process in the spray dryer, secondary aggregation due to the surface force of the volatile components is less likely to occur, and ultrafine composite tungsten oxide particles in which secondary aggregation is relatively unlikely to occur can be obtained even without performing a crushing process.
The composite tungsten oxide ultrafine particle dispersion as a near-infrared-absorbing-material ultrafine particle dispersion having high visible light transmittance and low solar transmittance due to the expression of the near-infrared-absorbing function and having optical characteristics such as a low haze value can be formed by dispersing the composite tungsten oxide ultrafine particles subjected to the drying treatment of (1) to (3) in a resin or the like by an appropriate method.
[d] Composite tungsten oxide ultrafine particle dispersion
The composite tungsten oxide ultrafine particle dispersion used for producing the agricultural and horticultural covering film of the present invention will be described.
The composite tungsten oxide ultrafine particle dispersion is prepared by mixing the composite tungsten oxide ultrafine particles obtained by the synthesis method; a liquid medium selected from water, an organic solvent, a liquid resin, a liquid plasticizer for plastics, a polymer monomer, or a mixed slurry of these; and a dispersant, a coupling agent, a surfactant and the like in an appropriate amount, and the mixture is pulverized and dispersed by a medium-stirring mill.
The fine particles in the solvent are dispersed in a good state, and the dispersion particle diameter is 1to 200 nm. The content of the composite tungsten oxide ultrafine particles contained in the composite tungsten oxide ultrafine particle dispersion is preferably 0.01 mass% or more and 80 mass% or less.
The composite tungsten oxide ultrafine particle dispersion of the present invention will be described below in the order of (1) the solvent, (2) the dispersant, (3) the dispersing method, (4) the dispersion particle size, (5) the binder, and other additives.
(1) Solvent(s)
The liquid solvent used for the composite tungsten oxide ultrafine particle dispersion is not particularly limited, and may be appropriately selected depending on the coating conditions and coating environment of the composite tungsten oxide ultrafine particle dispersion, and the inorganic binder, resin binder, and the like to be appropriately added. For example, the liquid solvent may be: water, an organic solvent, an oil or fat, a liquid resin, a liquid plasticizer for a dielectric resin, a polymer monomer, or a mixture thereof.
Here, as the organic solvent, for example, there can be selected: various solvents such as alcohols, ketones, hydrocarbons, glycols, and water. Specifically, it is possible to use: alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, diacetone alcohol, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl acetone, methyl isobutyl ketone, cyclohexanone, isophorone, and the like; ester solvents such as 3-methyl-methoxy-propionate; glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, and propylene glycol ethyl ether acetate; amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene and xylene; dichloroethane, chlorobenzene, and the like. Among these organic solvents, particularly preferred are: dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, and the like.
The fat or oil is preferably a vegetable fat or oil derived from a vegetable. As vegetable oils, there may be used: dry oil such as linseed oil, sunflower oil, tung oil, perilla oil, etc.; semi-dry oil such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, poppy oil, etc.; nondrying oils such as olive oil, coconut oil, palm oil, dehydrated castor oil, etc. As the compound derived from a vegetable oil, a fatty acid monoester obtained by directly subjecting a fatty acid of a vegetable oil and a monool to an ester reaction, an ether, or the like can be used. Further, commercially available petroleum solvents can be used as the oils and fats, and examples thereof include: ISOPAR E, EXXSOL Hexane, EXXSOL Heptane, EXXSOL E, EXXSOL D30, EXXSOL D40, EXXSOL D60, EXXSOL D80, EXXSOL D95, EXXSOL D110, EXXSOL D130 (all made by EXXON MOBIL), and the like.
As the liquid plasticizer for the dielectric resin, known liquid plasticizers represented by organic acid esters, phosphoric acid esters and the like can be used.
This is because the plasticity of the near-infrared-absorbing ultrafine particle dispersion can be improved by using the liquid plasticizer as a liquid medium in the composite tungsten oxide ultrafine particle dispersion for producing a near-infrared-absorbing ultrafine particle dispersion having plasticity.
Examples of the liquid plasticizer include: plasticizers which are compounds formed from monohydric alcohols and organic acid esters; plasticizers as esters such as polyol organic acid ester compounds; the plasticizer of phosphoric acid such as an organic phosphoric acid plasticizer is preferably liquid at room temperature. Among them, a plasticizer which is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferable.
The ester compound synthesized from a polyhydric alcohol and a fatty acid is not particularly limited, and examples thereof include: glycol ester compounds are obtained by reacting glycols such as triethylene glycol, tetraethylene glycol and tripropylene glycol with monobasic organic acids such as butyric Acid, isobutyric Acid, caproic Acid, 2-ethylbutyric Acid, heptanoic Acid, n-octanoic Acid, 2-ethylhexanoic Acid, n-nonanoic Acid (Pelargonic Acid) and decanoic Acid. Further, there may be mentioned: ester compounds formed by tetraethylene glycol, tripropylene glycol and the monobasic organic acid, and the like.
Among them, preferred are: triethylene glycol dihexanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol dicaprylate, triethylene glycol di-2-ethylhexanoate, and other fatty acid esters of triethylene glycol.
The polymer monomer is a monomer that forms a polymer by polymerization or the like, and preferable examples of the polymer monomer used in the present invention include: methyl methacrylate monomers, acrylate monomers, styrene resin monomers, and the like.
The liquid solvents described above may be used singly or in combination of two or more. Further, if necessary, an acid or a base may be added to these liquid solvents to adjust the pH.
(2) Dispersing agent
In addition, in order to further improve the dispersion stability of the composite tungsten oxide ultrafine particles in the composite tungsten oxide ultrafine particle dispersion and avoid coarsening of the dispersed particle diameter due to reagglomeration, it is preferable to add various dispersants, surfactants, coupling agents, and the like. The dispersant, the coupling agent, and the surfactant may be selected according to the intended use, and are preferably those having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups have the effect of preventing adsorption and aggregation on the surfaces of the composite tungsten oxide ultrafine particles and uniformly dispersing the composite tungsten oxide ultrafine particles of the present invention even in an infrared absorbing film. More preferably, the polymer-based dispersant has any of these functional groups in the molecule.
Preferred examples of the commercially available dispersant include: SOLSPERSE 3000, SOLSPERSE 9000, SOLSPERSE 11200, SOLSPERSE 13000, SOLSPERSE 13240, SOLSPERSE 13650, SOLSPERSE 13940, SOLSPERSE 16000, SOLSPERSE 17000, SOLSPERSE 18000, SOLSPERSE 20000, SOLSPERSE 21000, SOLSPERSE 24000SC, SOLSPERSE 24000GR, SOLSPERSE 26000, SOLSPERSE 27000, SOLSPERSE 28000, SOLSPERSE 31845, SOLSPERSE 32000, SOLSPERSE RSE 32500, SOLSPERSE 32550, SOLSPERSE 600, SOLSPERSE 3200, SOLSPERSE 33500, SOLSPERSE 5602, SOLSPERSE 32100, SOLSPERSE 35500, SOLSPERSE 3600, SOLSE 38500, SOLSE 36500, SOLSPERSERSE 3600, SOLSE 36567, SOLSPERSELSE 3600, SOLSE 36LSE 3600, SOLSE 35500, SOLSPERSELSE LSE 3600, SOLSE 36500, SOLSE LSE 3600, SOLSE 36500, SOLSPERSELSE 3600, SOLSE 36LSE 3600, SOLSE 36500, SOLSPERSELSE 3600, SOLSE 3200, SOLSE 36500, SOLSE 36LSE 36500, SOLSPERSELSE 36500, SOLSE 36LSE 3600, SOLSE 36LSE 3200, SOLSE 3, SOLSE LSE 36500, SOLSE 36LSE 3, SOLSE LSE 3, SOLSE LSE 3, SOLSE LSE 3, SOLSE LSE 3, SOLSE LSE 3, SOLSE LSE 3, SOLSE LSE 3, SOLSE LSE 3;
disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-108, Disperbyk-109, Disperbyk-110, Disperbyk-111, Disperbyk-112, Disperbyk-116, Disperbyk-130, Disperbyk-140, Disperbyk-142, Disperbyk-145, Disperbyk-154, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-167, Disperbyk-168, Disperbyk-170, Disperbyk-171, Disperbyk-174, Disperbyk-182, Disperbyk-181, Disperbyk-185, Disperbyk-181, Disperbyk-183, Disperbyk-181, Disperbyk-185, Disperbyk-181, Disperbyk-183, Disperbyk-181, Disperbyk-185, Disperbyk-181, Disperbyk-183, Disperbyk-181, Disperbyk-180, Disperbyk-181-180, Disperbyk-181, Disperbyk-181-183, Disperbyk-180, Disperbyk-181-183, Disperbyk-181-183, Disperbyk-181-180, Disperbyk-183, Disperbyk-181, Disperbyk-183, Disperbyk-180, Disperbyk-183, Disperbyk-181-185, Disperbyk-181, Disperbyk-183, Disperbyk-181-183, and Disperbyk-181-150, Disperbyk-183, Disperbyk-185, Disperbyk-183, Disperbyk-150, Disperbyk-181-183, Disperbyk-185, Disperbyk-150, Disperbyk-185, Disperbyk-2000, Disperbyk-183, Disperbyk-2000, Disperbyk-150, Disperbyk-2000, Disperbyk-150, Disperbyk-183, Disp, Anti-Terra-U, Anti-Terra-203, Anti-Terra-204, BYK-P104S, BYK-220S, BYK-6919, etc.;
EFKA4008, EFKA4046, EFKA4047, EFKA4015, EFKA4020, EFKA4050, EFKA4055, EFKA4060, EFKA4080, EFKA4300, EFKA4330, EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4500, EFKA4510, EFKA4530, EFKA4550, EFKA4560, EFKA4585, EFKA4800, EFKA5220, EFKA6230, JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL690, JONCRYL819, JONCRYL-355050, etc. manufactured by BASF JAPAN (stock);
AJISPER PB-711, AJISPER PB-821, AJISPER PB-822, and AJINOMOTO FINE-TECHNO, manufactured by AJINOMOTO CORPORATION.
(3) Dispersion method
By applying the composite tungsten oxide ultrafine particles to a substrate or kneading the composite tungsten oxide ultrafine particles into a substrate by an appropriate method, a near-infrared-absorbing ultrafine particle dispersion of a composite tungsten oxide ultrafine particle dispersion having a high visible light transmittance and a low solar transmittance and having a near-infrared-absorbing characteristic such as a low haze value can be formed.
The method of dispersing the composite tungsten oxide ultrafine particles in the dispersion liquid is not particularly limited as long as the fine particles can be uniformly dispersed in the dispersion liquid without aggregation. Examples of the dispersing method include: a method of pulverization and dispersion treatment using a device such as a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, or the like. Among them, from the viewpoint of a short time required for obtaining a desired dispersion particle diameter, pulverization and dispersion by a media agitation mill such as a bead mill, a ball mill, a sand mill, and a paint shaker using media such as beads, balls, and ottawa sand are preferable.
The composite tungsten oxide ultrafine particles can be dispersed in the dispersion by the pulverization/dispersion treatment using the medium-stirring mill, and the composite tungsten oxide ultrafine particles can be further pulverized and dispersed (that is, the pulverization/dispersion treatment is performed) by the collision of the composite tungsten oxide ultrafine particles with each other, the collision of the medium against the ultrafine particles, and the like at the same time.
In the pulverization and dispersion of the composite tungsten oxide ultrafine particles, when the XRD peak intensity value of the (220) plane of the silicon powder standard sample (640 c, manufactured by NIST) is 1, the process conditions for the pulverization and dispersion are set so that the ratio of the XRD peak top intensity of the composite tungsten oxide ultrafine particles can be secured to 0.13 or more. By this setting, an agricultural or horticultural covering film containing the composite tungsten oxide ultrafine particles exhibits excellent optical characteristics.
When the composite tungsten oxide ultrafine particles are dispersed in the plasticizer, an organic solvent having a boiling point of 120 ℃ or lower is further added as necessary, and this is also a preferable structure.
Specific examples of the organic solvent having a boiling point of 120 ℃ or lower include: toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropanol and ethanol. In particular, the material may be selected as long as it has a boiling point of 120 ℃ or lower and can uniformly disperse fine particles that exhibit a near-infrared ray absorption function. However, when this organic solvent is added, a drying step is performed after the dispersion is completed, and it is preferable that the organic solvent remaining in the infrared light absorption layer described below is 5 mass% or less as an example of the near-infrared light absorption ultrafine particle dispersion. When the residual solvent in the infrared light absorbing layer is 5% by mass or less, the following soil covering film for agriculture and horticulture does not generate bubbles, and maintains good appearance and optical characteristics.
(4) Dispersed particle size
The composite tungsten oxide ultrafine particles preferably have a dispersion particle diameter of 200nm or less, more preferably a dispersion particle diameter of 200nm or less and 10nm or more.
This is because, when the white light reflecting layer is provided in the earth covering film for agriculture and horticulture, it is necessary to consider the transparency of visible light when the infrared light absorbing layer is observed with naked eyes. Therefore, the infrared light absorption layer is required to efficiently absorb near infrared light while maintaining transparency of visible light.
Since the near-infrared absorbing component containing the composite tungsten oxide ultrafine particles of the present invention absorbs light in the near-infrared region, particularly, light having a wavelength of about 900 to 2200nm, the transmitted color tone in the visible light may be changed from a blue color system to a green color system. On the other hand, if the composite tungsten oxide ultrafine particles contained in the infrared absorption layer have a dispersion particle diameter of 1to 200nm, light in the visible light region having a wavelength of 380 to 780nm is not scattered by geometric scattering or mie scattering, and therefore color formation of the infrared absorption layer due to light scattering is reduced, and the purpose of increasing the visible light transmittance can be achieved. In addition, in the Rayleigh (Rayleigh) scattering region, since scattered light decreases in proportion to the sixth power of the particle size, scattering decreases and transparency improves as the dispersed particle size decreases. Therefore, when the dispersion particle diameter is set to 200nm or less, scattered light is extremely small, and transparency can be further increased, which is preferable.
From this fact, it is found that transparency can be secured by making the dispersed particle diameter of the ultrafine particles smaller than 200nm, and when importance is attached to the transparency, the dispersed particle diameter is preferably 150nm or less, more preferably 100nm or less. On the other hand, when the dispersed particle diameter is 1nm or more, industrial production is easy.
Here, the particle diameter of the composite tungsten oxide ultrafine particles dispersed in the composite tungsten oxide ultrafine particle dispersion will be briefly described. The dispersion particle diameter of the composite tungsten oxide ultrafine particles means a particle diameter of monomer particles of the composite tungsten oxide ultrafine particles dispersed in a solvent or a particle diameter of aggregated particles obtained by aggregating the composite tungsten oxide ultrafine particles, and can be measured by various commercially available particle size distribution meters. For example, a sample of the composite tungsten oxide ultrafine particle dispersion may be collected, and the sample may be measured using ELS-8000 manufactured by OTSUKA ELECTRONICS in which the principle of the dynamic light scattering method is used.
The composite tungsten oxide ultrafine particle dispersion having a composite tungsten oxide ultrafine particle content of 0.01 mass% to 80 mass% obtained by the above synthesis method is excellent in liquid stability. When a suitable liquid medium, dispersant, coupling agent, and surfactant are selected, the dispersion can be maintained at a temperature of 40 ℃ for 6 months or more without causing gelation of the dispersion or sedimentation of particles, and the dispersion particle diameter can be maintained within the range of 1to 200 nm.
The dispersion particle diameter of the composite tungsten oxide ultrafine particle dispersion may be different from the average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the near-infrared-absorbing-material ultrafine particle dispersion. This is because, even if the composite tungsten oxide ultrafine particles aggregate in the composite tungsten oxide ultrafine particle dispersion liquid, the aggregation of the composite tungsten oxide ultrafine particles is resolved when the near-infrared-absorbing-material ultrafine particle dispersion liquid is processed from the composite tungsten oxide ultrafine particle dispersion liquid.
(5) Binders and other additives
The composite tungsten oxide ultrafine particle dispersion may contain one or more selected from resin binders as appropriate. The type of the resin binder contained in the composite tungsten oxide ultrafine particle dispersion is not particularly limited, and as the resin binder, for example: thermoplastic resins such as acrylic resins, and thermosetting resins such as epoxy resins.
Further, in order to improve the near infrared ray absorption characteristics of the composite tungsten oxide ultrafine particle dispersion of the present invention, near infrared ray absorption ultrafine particles such as boride, ATO, and ITO represented by general formula XBm (wherein X is an alkaline earth element or a metal element selected from rare earth elements including yttrium; 4. ltoreq. m.ltoreq.6.3) are preferably added to the dispersion of the present invention as needed. The ratio of the additive in this case may be appropriately selected in accordance with the desired near infrared absorption characteristics.
In addition, in order to adjust the color tone of the composite tungsten oxide ultrafine particle dispersion, it is also possible to add: carbon black, bengal and other known inorganic pigments or known organic pigments.
A known ultraviolet absorber, a known infrared absorbing material of an organic substance, and a phosphorus-based stainblocker may be added to the composite tungsten oxide ultrafine particle dispersion.
[e] Soil covering film for agriculture and horticulture
The agricultural and horticultural mulch film of the present invention will be described.
Generally, sunlight reaching the ground surface has a wavelength range of about 290 to 2100nm, and visible light having a wavelength of about 380 to 780nm is necessary for plant growth. Therefore, by reflecting light in the visible wavelength region having a wavelength of about 380 to 780nm, near-infrared light having a wavelength of about 780 to 2100nm is selectively absorbed with good efficiency, light necessary for plant growth is reflected to plants, and hot infrared light is absorbed to warm the ground. When the agricultural or horticultural covering film is used in a greenhouse, etc., it is preferable that the atmosphere in the greenhouse does not increase in temperature.
Specifically, the agricultural and horticultural covering film of the present invention may have a structure in which an infrared light absorbing layer formed by coating ultrafine particles of an infrared absorbing material is provided on at least one surface of the agricultural and horticultural covering film, or may have a structure in which ultrafine particles of an infrared absorbing material are dispersedly present in the film of the agricultural and horticultural covering film.
The agricultural and horticultural covering film of the present invention may be provided with a white light reflecting layer in which a white light reflecting material is dispersed, or may be provided with an infrared light absorbing layer formed by coating ultrafine particles of an infrared absorbing material on at least one surface of the film provided with the white light reflecting layer.
Further, the white light reflecting layer and the infrared light absorbing layer may be formed by dispersing ultrafine particles of the white light reflecting material and the infrared light absorbing material in the film.
Further, a white light reflecting layer formed by applying a white light reflecting material on one surface of the film may be provided, and an infrared light absorbing layer formed by applying ultrafine particles of an infrared absorbing material on the white light reflecting layer may be provided.
Further, a white light reflecting layer formed by applying a white light reflecting material may be provided on one surface of the film, and an infrared light absorbing layer formed by applying ultrafine particles of an infrared absorbing material may be provided on the other surface of the film.
In the agricultural and horticultural mulch film of the present invention, the infrared light absorbing layer is not colored by the infrared light absorbing material ultrafine particles, and therefore, even if the white light reflecting layer is provided, the white light reflecting layer is not colored by the infrared light absorbing layer.
In the soil covering film for agriculture and horticulture, solar heat due to sunlight is absorbed by the infrared absorbing material ultrafine particles, infrared rays are absorbed by the film, the film temperature rises, and accordingly, radiant heat also increases, and the temperature inside the covered ground rises rapidly. In addition, when the soil covering film for agriculture and horticulture is used in a greenhouse or the like, the temperature of the atmosphere in the greenhouse or the like does not rise. In addition, in the case where the soil covering film for agriculture and horticulture is provided with the white light reflecting layer, since visible light is reflected by the white light reflecting material, the amount of light irradiated to plants increases, and the amount of photosynthesis increases, thereby promoting plant growth.
As a method of applying the ultrafine particles of the infrared absorbing material of the present invention, there is a method of forming an infrared absorbing layer dispersed in an appropriate medium, which is formed by applying the fine particles, on a surface of a desired substrate. Since this method can incorporate ultrafine particles of an infrared absorbing material obtained by firing at a high temperature in advance into a film substrate or bond the ultrafine particles to the surface of the substrate with a binder, the method can be applied to a substrate material having a low heat resistance temperature such as a resin material, does not require a large-scale apparatus for forming, and is inexpensive.
As described above, when the infrared light absorbing layer is formed by coating the ultrafine particles of the infrared light absorbing material on one surface of the film in which the white light reflecting material is partially dispersed, or a white light reflecting layer formed by applying a white light reflecting material on one surface of a film base material and an infrared light absorbing layer formed by applying ultrafine particles of an infrared absorbing material on the white light reflecting layer, or when a white light reflecting layer is formed by applying a white light reflecting material on one surface of a film base material and an infrared light absorbing layer is formed by applying ultrafine particles of an infrared absorbing material on the other surface, for example, when the ultrafine particles of the infrared absorbing material are dispersed in an appropriate solvent, after adding a resin binder thereto, the mixture is applied to the surface of a film substrate, a solvent is evaporated, and the resin is cured by a predetermined method, whereby a thin film in which the infrared absorbing material ultrafine particles are dispersed in a medium can be formed.
The method for applying the surface of the film substrate is not particularly limited as long as the resin containing the infrared absorbing material ultrafine particles can be uniformly applied to the surface of the film substrate, and examples thereof include: a bar coating method, a gravure coating method, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a screen printing method, a blade coating method, and the like. In addition, when the infrared absorbing material ultrafine particles are directly dispersed in the binder resin, evaporation of the solvent after application to the surface of the film base is not necessary, and therefore, the infrared absorbing material ultrafine particles are preferable in terms of environmental friendliness and industrial applicability.
The resin binder may be selected according to purposes, for example: UV curable resin, thermosetting resin, electron beam curable resin, normal temperature curable resin, thermoplastic resin, and the like.
Specific examples of the resin binder include: polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluororesin, polycarbonate resin, acrylic resin, polyvinyl butyral resin. In addition, a binder using a metal alkoxide may also be used. The metal alkoxide is represented by an alkoxide of Si, Ti, Al, Zr, or the like. The adhesive using these metal alkoxides can be hydrolyzed and heated to form an oxide film.
As described above, the infrared absorbing material ultrafine particles may be dispersed in the film base material in which the white light reflecting material is dispersed. The ultrafine particles may be dispersed in the base material by penetrating the surface of the base material, or may be melted by raising the temperature to a temperature higher than the melting temperature of the base material, and then the ultrafine particles of the infrared absorbing material may be mixed with the base resin. Alternatively, a master batch in which the ultrafine particles are contained in a base material resin at a high concentration may be prepared in advance, and the master batch may be diluted to a predetermined concentration. The resin containing ultrafine particles of an infrared absorbing material thus obtained is formed into a film by a predetermined method, and can be used as an infrared absorbing material.
The method for producing the master batch is not particularly limited, and for example, a mixture in which the above-mentioned ultrafine particles are uniformly dispersed in a thermoplastic resin can be adjusted by uniformly melt-mixing the composite tungsten oxide ultrafine particle dispersion, the powder or pellet of the thermoplastic resin, and other additives as needed, using a Mixer such as a Ribbon Mixer (Ribbon Blender), a tumbler, a Nauta Mixer (Nauta Mixer), a Henschel Mixer (Henschel Mixer), a high-speed Mixer, a planetary Mixer, and a kneader such as a Banbury Mixer (Banbury Mixer), a kneader, a roll, a kneading Mixer, a uniaxial extruder, or a biaxial extruder, while removing the solvent.
Further, the solvent of the composite tungsten oxide ultrafine particle dispersion may be removed by a known method, and the obtained powder, powder particles or granules of the thermoplastic resin, and other additives as necessary may be uniformly melt-mixed to prepare a mixture in which the ultrafine particles are uniformly dispersed in the thermoplastic resin. Further, a method of directly adding the powder of the composite tungsten oxide ultrafine particles to a thermoplastic resin and uniformly melt-mixing the mixture may be used.
The mixture obtained by the above method is kneaded by a vented uniaxial or biaxial extruder and processed into pellets, thereby obtaining a master batch containing a heat-absorbing component.
The method for dispersing the infrared absorbing material ultrafine particles in a resin is not particularly limited, and for example, the following can be used: ultrasonic dispersion, media agitation mills, ball mills, sand mills, and the like.
The dispersion medium of the infrared absorbing material ultrafine particles is not particularly limited, and may be selected in combination with the medium resin binder to be mixed, and for example, the following may be used: water, alcohols, ethers, esters, ketones, aromatic compounds and other common organic solvents. Further, if necessary, an acid or a base may be added to adjust the pH. In addition, various surfactants, coupling agents, and the like may be added to further improve the dispersion stability of the infrared absorbing material ultrafine particles.
The white light reflecting material used for the agricultural and horticultural covering film of the present invention is not particularly limited, and is preferably: TiO 22、ZrO2、SiO2、Al2O3、MgO、ZnO、CaCO3、BaSO4、ZnS、PbCO3And the like. These white light reflecting materials may be used alone or in combination of two or more.
In addition, from the viewpoint of improving the weather resistance of the infrared absorbing material, the surfaces of the ultrafine particles constituting the infrared absorbing material used for the earth-covering film for agriculture and horticulture of the present invention are preferably coated with an oxide containing at least one kind selected from Si, Ti, Zr, and Al. These oxides are substantially transparent and do not cause a decrease in visible light transmittance by addition. The coating method is not particularly limited, and the surface of the infrared absorbing material ultrafine particles can be coated by adding the alkoxide of the metal to a solution in which the infrared absorbing material ultrafine particles are dispersed.
The film used for the agricultural and horticultural covering film of the present invention is not particularly limited, and examples thereof include: polyethylene, polypropylene, polyethylene terephthalate, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, ethylene vinyl acetate, polyester resin, and the like. Among these resins, it is also possible to add: stabilizers, stabilizing aids, antioxidants, plasticizers, slip agents, ultraviolet absorbers, and the like.
Accordingly, the agricultural and horticultural covering film of the present invention is a film provided with a white light reflecting layer containing a white light reflecting material and an infrared light absorbing layer containing ultrafine particles of an infrared absorbing material, and the infrared light absorbing layer containing ultrafine particles of an infrared absorbing material, preferably composite tungsten oxide, is formed by a simple method, thereby providing an agricultural and horticultural covering film which has good weather resistance and low cost, and can efficiently absorb near infrared rays from sunlight and reflect visible rays with a small amount of ultrafine particles.
When the film is used for a ground surface for growing plants or the like, the temperature of the ground surface to be covered is raised to warm the ground, and when the soil covering film for agriculture and horticulture is used in a greenhouse or the like, there is an effect that the temperature of the atmosphere in the greenhouse or the like is not raised.
In addition, in the case where the white light reflecting layer is provided on the agricultural and horticultural mulch film, since visible light is reflected by the white light reflecting material, the amount of light irradiated to the plant is increased, and the amount of photosynthesis is increased, thereby promoting the growth of the plant.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
The optical properties of the dispersion and the coating film in the examples and comparative examples were measured using a spectrophotometer (U-4100, manufactured by Hitachi Ltd.), and the visible light transmittance and the solar transmittance were calculated in accordance with JIS R3106. The dispersed particle size is represented by an average value measured by a particle size measuring apparatus (ELS-8000, manufactured by OTSUKA ELECTRONICS Co., Ltd.) by a dynamic light scattering method.
In addition, for the volatile component content of the examples and comparative examples, a water content meter manufactured by Shimadzu corporation; MOC63u, increased from room temperature to 125 ℃ within 1 minute from the start of measurement of the sample, and held at 125 ℃ for 9 minutes. Then, the weight reduction rate of the measurement sample 10 minutes after the start of the measurement was defined as the content rate of the volatile component. The average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the infrared absorption film was measured by observing a transmission electron microscope image of a cross section of the absorption film.
The transmission electron microscope image was observed using a transmission electron microscope (HITACHI HIGH-HF-2200, manufactured by TECHNOLOGIES GmbH). The transmission electron microscope image was processed by an image processing apparatus, and the particle diameters of 100 composite tungsten oxide particles were measured, and the average value thereof was defined as the average particle diameter.
The X-ray diffraction pattern was measured by a powder X-ray diffraction method (theta-2 theta method) using a powder X-ray diffraction apparatus (X' Pert-PRO/MPD, product of PANALYtic, Inc., SPECTRIS Co., Ltd.). In addition, in order to ensure objective quantitativity, X-ray diffraction pattern measurement of a silicon powder standard sample was performed every time the X-ray diffraction pattern was measured for the composite tungsten oxide ultrafine particles, and the ratio of peak intensities for each time was calculated.
[ example 1]
0.216kg of Cs was dissolved in 0.330kg of water2CO3It was added to 1.000kg of H2WO4Fully stirring the mixture, and drying the mixture to obtain the target composition Cs0.33WO3The mixed powder of (1).
Next, using the high-frequency plasma reaction apparatus described in fig. 1, the inside of the reaction system was evacuated to about 0.1Pa (about 0.001Torr) by a vacuum evacuation apparatus, and then completely replaced with argon gas to form a flow system of 1 pressure. Then, argon gas as a plasma gas was introduced into the reaction vessel at a flow rate of 30L/min, and a sheath gas was introduced spirally from a sheath gas supply port at flow rates of 55L/min and 5L/min of helium gas. Then, high-frequency power was applied to a water-cooled copper coil for generating high-frequency plasma, thereby generating high-frequency plasma. In this case, the high-frequency power is set to 40kW so that thermal plasma having a high-temperature portion of 10000 to 15000K can be generated.
Thus, after the high-frequency plasma was generated, the mixed powder was supplied to the thermal plasma at a rate of 50g/min while supplying argon gas as a carrier gas from the gas supply device 11 at a flow rate of 9L/min.
As a result, the mixed powder is instantaneously evaporated in the thermal plasma, and rapidly solidified and ultrafinely pulverized in the process of reaching the plasma tail flame portion. The produced ultrafine particles are deposited on a recovery filter.
The production conditions are shown in table 1. Table 1 also shows the production conditions of examples 2 to 13 below.
The deposited ultrafine particles were collected, and an X-ray diffraction pattern was measured by a powder X-ray diffraction method (theta-2 theta method) using a powder X-ray diffraction apparatus (X' Pert-PRO/MPD manufactured by PANALYtic, Inc., SPECTRIS Co., Ltd.).
The X-ray diffraction pattern of the obtained ultrafine particles is shown in FIG. 2. Performing phase identification, and identifying the obtained superfine particles as hexagonal crystal Cs0.33WO3A single phase. Further, the crystal structure of the ultrafine particles was analyzed by Rietveld analysis using the X-ray diffraction pattern, and as a result, the crystallite diameter of the obtained ultrafine particles was 18.8 nm. Further, the peak top intensity value of the X-ray diffraction pattern of the obtained ultrafine particles was 4200 counts.
The composition of the obtained ultrafine particles was examined by ICP emission analysis. As a result, the Cs concentration was 13.6 mass%, the W concentration was 65.3 mass%, and the Cs/W molar ratio was 0.29. The remainder except Cs and W was oxygen, and it was confirmed that no other impurity element was contained by 1 mass% or more.
The BET specific surface area of the obtained ultrafine particles was measured to be 60.0m by a BET specific surface area measuring apparatus (HMmodel-1208, MOUNTECH Co., Ltd.)2(ii) in terms of/g. Nitrogen gas having a purity of 99.9% was used for measuring the BET specific surface area.
The content of volatile components in the composite tungsten oxide ultrafine particles of example 1 was 1.6 mass%.
10 parts by weight of the obtained composite tungsten oxide ultrafine particles, 80 parts by weight of toluene, and 10 parts by weight of an acrylic polymer dispersant having an amine-containing group as a functional group (an acrylic dispersant having an amine value of 48mgKOH/g and a decomposition temperature of 250 ℃) (hereinafter referred to as "dispersant a") were mixed to prepare 3kg of slurry. The slurry was put into a medium-stirring mill together with beads, and pulverized and dispersed for 0.5 hour. The media-stirring mill used was a horizontal cylindrical ring type (manufactured by ASHIZAWA FINETECH corporation), and the material of the inner wall of the vessel and the rotor (rotating stirring part) was zirconia. Further, as the beads, those made of YSZ (Yttria-Stabilized Zirconia: gadolinium Stabilized Zirconia) having a diameter of 0.1mm were used. The composite tungsten oxide ultrafine particle dispersion of example 1 was obtained by pulverizing and dispersing the above-mentioned powder at a slurry flow rate of 0.5kg/min with the rotation speed of the rotor set at 14 rpm/sec.
The X-ray diffraction pattern of the composite tungsten oxide ultrafine particles contained in the composite tungsten oxide ultrafine particle dispersion liquid of example 1, i.e., the composite tungsten oxide ultrafine particles after the pulverization and dispersion treatment, had a peak top intensity value of 3000 counts and a peak position of 2 θ of 27.8 °.
On the other hand, a silicon powder standard sample (manufactured by NIST, 640c) was prepared, and the peak intensity value based on the (220) plane in the silicon powder standard sample was measured, and the number thereof was 19800.
As can be seen from this, assuming that the peak intensity value of the standard sample is 1, the ratio of the XRD peak intensity of the composite tungsten oxide ultrafine particles after the pulverization and dispersion treatment in example 1 is 0.15.
The composite tungsten oxide ultrafine particles obtained by the pulverization and dispersion treatment in example 1 had a crystallite diameter of 16.9 nm.
The dispersed particle size of the composite tungsten oxide ultrafine particle dispersion of example 1 was measured to be 70nm using a particle size measuring apparatus based on a dynamic light scattering method. As the setting for the particle size measurement, the refractive index of the particles was 1.81, and the particle shape was non-spherical. The background was measured using toluene, and the refractive index of the solvent was 1.50.
The results are shown in Table 3. In addition, the results obtained in the following examples 2 to 13 are also shown in Table 3.
50 parts by weight of the composite tungsten oxide ultrafine particle dispersion of example 1 and an ultraviolet-curable resin for hard coating(solid content 100%) 30 parts by weight to obtain an infrared absorbing material ultrafine particle dispersion body fluid. The infrared absorbing material ultrafine particle dispersion liquid is coated on a TiO-containing material by a bar coater2The white light reflecting material is formed by coating fine particles on a polyethylene film. The film was dried at 60 ℃ for 30 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp to obtain the infrared absorbing film of example 1 having a high diffuse reflectance in the visible light region.
The average particle size of the composite tungsten oxide ultrafine particles dispersed in the infrared absorbing film of example 1 thus prepared was 17nm, which is substantially the same as the crystallite particle size of 16.9nm, as calculated by an image processing apparatus using a transmission electron microscope image.
The spectral characteristics of the film thus prepared were measured by transmittance of light having a wavelength of 200 to 2600nm using a spectrophotometer manufactured by hitachi, and the visible light transmittance, the solar transmittance, the visible light reflectance, the solar reflectance, and the solar absorptance were calculated according to JIS a 5759. (here, the solar absorptance is calculated from 100% solar absorptance (%) -100% solar transmittance (%) -solar reflectance (%).
The results are shown in Table 5. In addition, the results obtained in the following examples 2 to 13 are also shown in Table 5.
[ examples 2 to 6]
Except for changing the carrier gas flow rate, the plasma gas flow rate, the sheath flow rate, and the raw material supply rate, the composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle dispersions of examples 2 to 6 were produced in the same manner as in example 1. The carrier gas flow rate conditions, raw material supply rate conditions, and other conditions were changed as shown in table 1. The composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle dispersion of examples 2 to 6 were evaluated in the same manner as in example 1.
The evaluation results are shown in table 2.
The infrared absorbing films of examples 2 to 6 were obtained and evaluated in the same manner as in example 1, except that the composite tungsten oxide ultrafine particle dispersions of examples 2 to 6 were used.
The results are shown in tables 1, 3 and 5.
[ example 7]
Cs described in example 12CO3And H2WO4The mixed powder of (3) is fired at 800 ℃ in a mixed gas atmosphere of nitrogen and hydrogen to convert into Cs0.33WO3The composite tungsten oxide is used as a raw material to be charged into a high-frequency plasma reaction apparatus. Except for this, the composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle dispersion of example 7 were produced in the same manner as in example 1. The obtained ultrafine particles and the dispersion thereof were evaluated in the same manner as in example 1. The production conditions and the evaluation results are shown in tables 1 and 2.
An infrared absorbing film of example 7 was obtained and evaluated in the same manner as in example 1, except that the composite tungsten oxide ultrafine particle dispersion of example 7 was used.
The results are shown in tables 1, 3 and 5.
[ example 8]
A dispersion of the composite tungsten oxide ultrafine particles and the composite tungsten oxide ultrafine particle of example 8 was produced in the same manner as in example 7, except that the flow rate of the carrier gas and the raw material supply rate were changed. The obtained ultrafine particles and the dispersion thereof were evaluated in the same manner as in example 1. The production conditions and the evaluation results are shown in tables 1 and 2.
An infrared absorbing film of example 8 was obtained and evaluated in the same manner as in example 1, except that the composite tungsten oxide ultrafine particle dispersion of example 8 was used.
The results are shown in tables 1, 3 and 5.
[ examples 9 to 13]
Dissolving 0.148kg of Rb in 0.330kg of water2CO3It was added to 1.000kg of H2WO4In the preparation method, the Rb is obtained by fully stirring and drying the mixture to obtain the target composition Rb0.32WO3The mixed powder of example 9.
0.375kg of K was dissolved in 0.330kg of water2CO3It was added to 1.000kg of H2WO4After fully stirring, drying to obtain the target composition K0.27WO3The mixed powder of example 10.
0.320kg of TlNO was dissolved in 0.330kg of water3It was added to 1.000kg of H2WO4After fully stirring, drying to obtain the target composition Tl0.19WO3The mixed powder of example 11.
0.111kg of BaCO was dissolved in 0.330kg of water3It was added to 1.000kg of H2WO4After fully stirring, drying to obtain the target composition Ba0.14WO3The mixed powder of example 12.
0.0663kg of K were dissolved in 0.330kg of water2CO3With 0.0978kg of Cs2CO3It was added to 1.000kg of H2WO4After fully stirring, drying to obtain the target composition K0.24Cs0.15WO3The mixed powder of example 13.
Except that the mixed powders of examples 9 to 13 were used as raw materials to be charged into a high-frequency thermal plasma reaction apparatus, composite tungsten oxide ultrafine particles and composite tungsten oxide ultrafine particle dispersions of examples 9 to 13 were produced in the same manner as in example 1. The obtained ultrafine particles and the dispersion thereof were evaluated in the same manner as in example 1. The production conditions and the evaluation results are shown in tables 1 and 2.
The infrared absorbing films of examples 9 to 13 were obtained and evaluated in the same manner as in example 1, except that the composite tungsten oxide ultrafine particle dispersions of examples 9 to 13 were used.
The results are shown in tables 1, 3 and 5.
[ example 14]
10.8g of Cs were dissolved in 16.5g of water2CO3This solution was added to 50g of H2WO4In the preparation method, the mixture is fully stirred and driedAnd (5) drying. N is supplied to the dried product22% H with gas as carrier2The mixture was heated at 800 ℃ for 30 minutes while being heated. Then, using at N2The composite tungsten oxide of example 14 was obtained by a solid phase method in which firing was performed at 800 ℃ for 90 minutes in a gas atmosphere.
Except for this, a composite tungsten oxide ultrafine particle dispersion of example 14 was produced in the same manner as in example 1. However, the time for the pulverization and dispersion treatment by the media-stirring mill was set to 2 hours. The obtained ultrafine particles and a dispersion thereof were evaluated in the same manner as in example 1.
The X-ray diffraction pattern of the obtained ultrafine particles was measured and the phase identification was performed, and the obtained ultrafine particles were identified as hexagonal Cs0.33WO3A single phase.
The production conditions are shown in table 2. Table 2 also shows the production conditions of examples 15 to 26 and comparative examples 1to 4 below.
The evaluation results are shown in table 4. In addition, the results obtained in examples 15 to 26 and comparative examples 1to 4 described below are also shown in Table 4.
An infrared absorbing film of example 14 was obtained and evaluated in the same manner as in example 1, except that the composite tungsten oxide ultrafine particle dispersion of example 14 was used.
The evaluation results are shown in table 6. Table 6 also shows the results obtained in examples 15 to 26 and comparative examples 1to 5 below.
[ example 15]
0.216kg of Cs was dissolved in 0.330kg of water2CO3The resulting solution was added to 1.000kg of H2WO4After sufficiently stirring, the mixture was dried to obtain a dried product. One side is supplied with N25% H with gas as carrier2The dried product was fired at 800 ℃ for 1 hour while heating with a gas. Then, further in N2A composite tungsten oxide of example 15 was obtained by a solid-phase reaction method in which firing was performed at 800 ℃ for 2 hours in a gas atmosphere.
The obtained 10 parts by weight of the composite tungsten oxide of example 15 was mixed with 90 parts by weight of water to prepare about 3kg of slurry. The slurry was not added with a dispersant. The slurry was put into a medium-stirring mill together with beads, and pulverized and dispersed for 2 hours. The media-stirring mill used was a horizontal cylindrical ring type (manufactured by ASHIZAWA FINETECH corporation), and the material of the inner wall of the vessel and the rotor (rotating stirring part) was zirconia. Further, as the beads, those made of YSZ (Yttria-Stabilized Zirconia: gadolinium Stabilized Zirconia) having a diameter of 0.1mm were used. The composite tungsten oxide ultrafine dispersion of example 15 was obtained by pulverizing and dispersing the above-mentioned powder at a slurry flow rate of 0.5kg/min at a rotor rotation speed of 14 rpm/sec.
The particle size of the composite tungsten oxide ultrafine particle aqueous dispersion of example 15 was measured to be 70 nm. In the measurement of the dispersed particle size, the refractive index of the particles was set to 1.81, and the shape of the particles was non-spherical. The background was measured using water, and the refractive index of the solvent was 1.33.
Then, about 3kg of the obtained composite tungsten oxide ultrafine particle dispersion was dried by an air dryer, to obtain composite tungsten oxide ultrafine particles of example 15. The air dryer used was a constant temperature oven (SPH-201 model manufactured by ESPEC corporation), and the drying temperature was 70 ℃ and the drying time was 96 hours.
The X-ray diffraction pattern of the ultrafine composite tungsten oxide particles of example 15 was measured, and the resulting ultrafine particles were identified as hexagonal Cs0.33WO3A single phase. The peak intensity of the X-ray diffraction pattern of the obtained ultrafine particles was 4200 counts, the peak position was 27.8 °, and the crystallite diameter was 23.7 nm. On the other hand, a silicon powder standard sample (manufactured by NIST, 640c) was prepared, and the number of the peak intensity values based on the (220) plane in the silicon powder standard sample was measured to obtain a 19800 count. As can be seen from this, assuming that the peak intensity value of the standard sample is 1, the ratio of the XRD peak intensities of the ultrafine composite tungsten oxide particles obtained after the pulverization and dispersion treatment in example 15 is0.21。
The composition of the obtained ultrafine composite tungsten oxide particles of example 15 was examined by ICP emission spectrometry. As a result, the Cs concentration was 15.2 mass%, the W concentration was 64.6 mass%, and the Cs/W molar ratio was 0.33. The remainder except Cs and W is oxygen. Further, it was confirmed that other impurity elements containing 1 mass% or more were not present.
The BET specific surface area of the ultrafine composite tungsten oxide particles of example 15 obtained after pulverization was measured to be 42.6m2/g。
The content of volatile components in the composite tungsten oxide ultrafine particles of example 15 was measured to be 2.2 mass%.
10 parts by weight of the obtained composite tungsten oxide ultrafine particles were dispersed in 80 parts by weight of toluene and 10 parts by weight of a dispersant a in a solvent to prepare 50g of a dispersion, and the dispersion particle diameter of the dispersion was 80nm as a result of measurement. In the measurement of the dispersed particle size, the refractive index of the particles was set to 1.81, and the shape of the particles was non-spherical. The solution was diluted with toluene and measured, and the refractive index of the solvent was 1.50.
An infrared-absorbing material ultrafine particle dispersion liquid was prepared by mixing 50 parts by weight of the composite tungsten oxide ultrafine particle dispersion liquid of example 15 with 30 parts by weight of an ultraviolet-curable resin for hard coating (solid content: 100%). The infrared absorbing material ultrafine particle dispersion liquid is coated on a TiO-containing material by a bar coater2The white light reflecting material is formed by coating fine particles on a polyethylene film. The film was dried at 60 ℃ for 30 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp to obtain the infrared absorbing film of example 15 having a high diffuse reflectance in the visible region.
The average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the infrared absorbing film of example 15 thus prepared was 23nm, which was substantially the same as the crystallite particle diameter of 23.7nm, as calculated by an image processing apparatus using a transmission electron microscope image.
The spectral characteristics of the film thus prepared were measured by transmittance of light having a wavelength of 200 to 2100nm using a spectrophotometer manufactured by hitachi, and the visible light transmittance, the solar transmittance, the visible light reflectance, the solar reflectance, and the solar absorptance were calculated according to JIS a 5759. (here, the solar absorptance is calculated from 100% -solar transmittance (%) -solar reflectance (%).
The results are shown in tables 2, 4 and 6.
[ example 16]
An infrared absorbing film of example 16 was obtained and evaluated in the same manner as in example 15, except that the drying treatment by the atmospheric dryer was changed to the vacuum drying treatment by the vacuum kneading and mashing machine.
The results are shown in tables 2, 4 and 6.
The vacuum kneading and mashing machine used was a Kagawa type kneading and mashing machine 24P (manufactured by Takawa chemical mechanical Co., Ltd.), and the drying temperature in the vacuum drying treatment was 80 ℃ and the drying time was 32 hours, the rotational frequency of the kneading mixer was 40Hz, and the pressure in the vacuum vessel was 0.001MPa or less.
[ example 17]
An infrared absorbing film of example 17 was obtained and evaluated in the same manner as in example 15, except that the drying treatment by the air dryer was changed to the spray drying treatment by the spray dryer.
The results are shown in tables 2, 4 and 6.
The spray dryer used was a spray dryer model ODL-20 (manufactured by Dachuan Processingequipment Co., Ltd.).
[ examples 18 to 20]
The infrared absorbing films of examples 18 to 20 were obtained and evaluated in the same manner as in examples 15 to 17 except that the time for the pulverization and dispersion treatment by the media-stirring mill was changed to 1 hour.
The results are shown in tables 2, 4 and 6.
[ examples 21 to 23]
Infrared absorbing films of examples 21 to 23 were obtained and evaluated in the same synthetic production method as in examples 15 to 17, except that 10 parts by weight of the composite tungsten oxide was mixed with 90 parts by weight of propylene glycol monoethyl ether as a solvent in the preparation of the ultrafine composite tungsten oxide particle dispersion.
The results are shown in tables 2, 4 and 6.
[ example 24]
Composite tungsten oxide ultrafine particles were obtained in the same manner as in example 1. Then, 10 parts by weight of the obtained ultrafine particles, 80 parts by weight of toluene, and 10 parts by weight of a dispersant were mixed to prepare 50g of slurry. This slurry was subjected to a dispersion treatment for 0.5 hour using an ultrasonic homogenizer (US-600 TCVP, manufactured by Nippon Seiko Co., Ltd.) to obtain a composite tungsten oxide ultrafine particle dispersion of example 24, and an infrared absorbing film of example 24 was obtained and evaluated in the same manner as in example 1.
The results are shown in tables 2, 4 and 6.
[ example 25]
Toluene was removed from the composite tungsten oxide ultrafine particle dispersion liquid of example 1 using a spray dryer, and composite tungsten oxide ultrafine particle dispersed powder of example 25 was obtained.
The obtained composite tungsten oxide ultrafine particle dispersion powder was added to polyethylene resin particles, uniformly mixed by a blender, melt kneaded by a twin-screw extruder, and the extruded strands were cut into particles to obtain a master batch containing composite tungsten oxide ultrafine particles.
In the same manner, a product containing TiO is obtained2The master batch of (1).
The master batch containing the composite tungsten oxide superfine particles and the master batch containing TiO2The master batch of (3) is mixed with a master batch prepared in the same manner without adding inorganic fine particles. The compounded master batch was extrusion-molded to form a film having a thickness of 50 μm.
The results are shown in tables 2, 4 and 6.
[ example 26]
50 parts by weight of the composite tungsten oxide ultrafine particle dispersion of example 1 and 30 parts by weight of an ultraviolet-curable resin for hard coating (solid content: 100%) were mixed to prepare a mixtureForming an infrared absorbing material ultrafine particle dispersion body fluid. According to the same method, the product containing TiO is obtained2The fine white light reflecting material fine particles disperse the body fluid. The infrared absorbing material ultrafine particle dispersion liquid was applied to a polyethylene film by a bar coater to form a film. The film was dried at 60 ℃ for 30 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp. Then, on the other surface of the polyethylene film, white light reflecting material fine particles were applied in the same manner to form a film, and the film was cured to obtain an infrared absorbing film having a high diffuse reflectance in the visible light region.
The results are shown in tables 2, 4 and 6.
[ comparative examples 1to 2]
Infrared absorbing films of comparative examples 1 and 2 were obtained and evaluated in the same manner as in example 1, except that the carrier gas flow rate, the plasma gas flow rate, the sheath fluid flow rate, and the raw material supply rate were changed.
The results are shown in tables 2, 4 and 6.
Comparative example 3
An infrared absorbing film of comparative example 3 was obtained and evaluated in the same manner as in example 1, except that the high-frequency power was set to 15kW in order to generate thermal plasma having a high-temperature portion of 5000 to 10000K.
The results are shown in tables 2, 4 and 6.
Comparative example 4
An aqueous dispersion of ultrafine composite tungsten oxide particles of comparative example 4 was obtained in the same manner as in example 15, except that the aqueous dispersion of ultrafine composite tungsten oxide particles of example 15 was subjected to pulverization and dispersion treatment for 20 hours, which was performed for 2 hours. The particle size of the composite tungsten oxide ultrafine particle aqueous dispersion of comparative example 4 was measured to be 120 nm. In the measurement of the dispersed particle size, the refractive index of the particles was set to 1.81, and the shape of the particles was non-spherical. The background was measured using water, and the refractive index of the solvent was 1.33.
X-ray diffraction pattern of ultrafine composite tungsten oxide particles of comparative example 4 was measured and phase identification was performedAs a result, the obtained ultrafine particles were identified as hexagonal Cs0.33WO3A single phase. The X-ray diffraction pattern of the obtained ultrafine particles had a peak intensity value of 1300 counts, a peak position of 27.8 ° 2 θ, and a crystallite particle diameter of 8.1 nm. On the other hand, a silicon powder standard sample (manufactured by NIST, 640c) was prepared, and the number of the peak intensity values based on the (220) plane in the silicon powder standard sample was measured to obtain a 19800 count. As can be seen from this, assuming that the peak intensity value of the standard sample is 1, the ratio of the XRD peak intensity of the ultrafine composite tungsten oxide particles after the pulverization and dispersion treatment in example 1 is 0.07.
The BET specific surface area of the ultrafine composite tungsten oxide particles of comparative example 4 obtained by the pulverization was measured to be 102.8m2/g。
The content of volatile components in the composite tungsten oxide ultrafine particles of comparative example 4 was measured, and the result was 2.2 mass%.
10 parts by weight of the obtained composite tungsten oxide ultrafine particles were dispersed in 80 parts by weight of toluene and 10 parts by weight of a dispersant, to obtain 50g of a composite tungsten oxide ultrafine particle dispersion of comparative example 4. Then, the dispersed particle size of the composite tungsten oxide ultrafine particle dispersion was measured to be 120 nm. In the measurement of the dispersed particle size, the refractive index of the particles was set to 1.81, and the shape of the particles was non-spherical. The background was measured using toluene, and the refractive index of the solvent was 1.50.
50 parts by weight of the composite tungsten oxide ultrafine particle dispersion of comparative example 4 and 30 parts by weight of an ultraviolet-curable resin for hard coating (solid content: 100%) were mixed to prepare an infrared-absorbing material ultrafine particle dispersion liquid. The infrared absorbing material ultrafine particle dispersion liquid is coated on a TiO-containing material by a bar coater2The white light reflecting material is formed by coating fine particles on a polyethylene film. The film was dried at 60 ℃ for 30 seconds to evaporate the solvent, and then cured by a high-pressure mercury lamp to obtain an infrared absorbing film of comparative example 4.
The average particle diameter of the composite tungsten oxide ultrafine particles dispersed in the infrared absorption film of comparative example 4 thus prepared was calculated to be 120nm by an image processing apparatus using a transmission electron microscope image, which is a value different from the crystallite particle diameter of 8.1 nm.
The spectral characteristics of the prepared film were measured by transmittance of light having a wavelength of 200 to 2100nm using a spectrophotometer manufactured by hitachi, and the visible light transmittance, the solar transmittance, the visible light reflectance, the solar reflectance, and the solar absorptance (here, the solar absorptance was calculated from 100% solar transmittance (%) to solar reflectance (%) in accordance with JIS a 5759) were calculated.
The results are shown in tables 2, 4 and 6.
Comparative example 5
Measuring body fluid of ultrafine particle dispersion of uncoated infrared absorbing material and containing TiO2The fine particles have spectral characteristics of a polyethylene film as a white light reflecting material.
The results are shown in Table 6.
[ conclusion ]
As is clear from table 2, the composite tungsten oxide ultrafine particles contained in the infrared absorbing films of examples 1to 27 had a ratio of XRD peak top intensity to XRD peak intensity value on the surface of (220) of the silicon powder standard sample (manufactured by NIST, 640c) of 0.13 or more, and had a crystallite diameter of 1nm or more.
Here, since the average particle size of the composite tungsten oxide ultrafine particles in the infrared absorbing film in the examples is substantially the same as the crystallite particle size, it is considered that the composite tungsten oxide ultrafine particles used are single-crystal composite tungsten oxide ultrafine particles having an amorphous phase volume ratio of 50% or less.
On the other hand, the average particle size of the composite tungsten oxide ultrafine particles in the infrared absorbing films of comparative examples 1, 2, and 4 was larger than the crystallite particle size, and it was considered that the film was not a single crystal. Furthermore, a heterogeneous phase was generated in comparative example 3 (WO)2And W).
As can be seen from table 3, when examples 1to 26 and comparative examples 1to 4 were compared, it was found that the infrared absorption rate of the film was significantly increased, the visible light was reflected, and the heat storage property was excellent by forming an infrared light absorbing layer formed by coating composite tungsten oxide ultrafine particles on the film in which the white light reflecting material was dispersed. That is, it is found that the reflectance of visible light is kept at approximately 6 to 7, and the solar absorptance is increased by about 4 to 6 in examples 1to 26.
The agricultural and horticultural covering film of the present invention is a film provided with a white light reflecting layer containing a white light reflecting material and an infrared light absorbing layer containing ultrafine particles of an infrared absorbing material, and specifically, a film in which the white light reflecting material is dispersed in the white light reflecting layer. And, there are: a film having a structure in which an infrared light absorbing layer is formed by coating ultrafine particles of an infrared absorbing material on one surface of the film; a film having a structure in which the white light reflecting layer and the infrared light absorbing layer are formed by dispersing ultrafine particles of a white light reflecting material and an infrared light absorbing material in the film; the film may have a white light reflecting layer formed by applying a white light reflecting material on one surface of the film, an infrared light absorbing layer formed by further applying ultrafine particles of an infrared absorbing material on the white light reflecting layer, a white light reflecting layer formed by applying a white light reflecting material on one surface of the film, and an infrared light absorbing layer formed by applying ultrafine particles of an infrared absorbing material on the other surface of the film.
The infrared light absorbing layer containing the composite tungsten oxide ultrafine particles as the infrared light absorbing material ultrafine particles is formed by such a simple method, and an agricultural and horticultural covering film having high weather resistance and low cost and capable of efficiently absorbing near infrared rays from sunlight with a small amount of fine particles can be provided.
Figure GDA0003261409300000391
Figure GDA0003261409300000401
Figure GDA0003261409300000411
[ Table 4]
Figure GDA0003261409300000421
[ Table 5]
Figure GDA0003261409300000422
[ Table 6]
Figure GDA0003261409300000431
Description of the symbols
1 thermal plasma
2 high-frequency coil
3 sheath gas supply nozzle
4 plasma gas supply nozzle
5 raw material powder supply nozzle
6 reaction vessel
7 suction tube
8 Filter

Claims (13)

1. An agricultural and horticultural covering film having an infrared light absorbing layer containing ultrafine particles of an infrared absorbing material, wherein,
the infrared absorption material ultrafine particles are composite tungsten oxide ultrafine particles,
the composite tungsten oxide ultrafine particles are as follows: composite tungsten oxide ultrafine particles having an XRD peak intensity ratio of 0.13 or more, where 1 is an XRD peak intensity value on the 220 plane of silicon powder standard sample 640c manufactured by NIST.
2. The agricultural and horticultural covering film according to claim 1, wherein an infrared light absorbing layer in which the infrared absorbing material ultrafine particles are dispersed in a resin binder is provided on at least one surface of the agricultural and horticultural covering film.
3. The agricultural and horticultural covering film according to claim 1, wherein the infrared absorbing material ultrafine particles are present dispersedly inside the film of the agricultural and horticultural covering film.
4. The agricultural or horticultural covering film according to claim 1, wherein the composite tungsten oxide ultrafine particles have a crystallite diameter of 1nm or more and 200nm or less.
5. The agricultural and horticultural covering film according to claim 1, wherein the composite tungsten oxide ultrafine particles are represented by a general formula MxWyOz, wherein M is at least one element selected from the group consisting of H, He, alkali metals, alkaline earth metals, rare earth elements, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Hf, Os, Bi, I, W is tungsten, O is oxygen, and x, y, and z satisfy 0.001. ltoreq. x/y.ltoreq.1, and 2.0< z/y.ltoreq.3. 0.
6. The agricultural and horticultural covering film according to claim 1, wherein the composite tungsten oxide ultrafine particles have a hexagonal crystal structure.
7. The agricultural and horticultural covering film according to claim 5, wherein the alkaline earth metal is Mg or Be, and the rare earth element is Yb.
8. The agricultural and horticultural covering film according to claim 1, wherein the surfaces of the composite tungsten oxide ultrafine particles are coated with an oxide containing at least one element selected from the group consisting of Si, Ti, Zr and Al.
9. The agricultural and horticultural covering film according to claim 1, wherein the film is at least one or more selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, ethylene-vinyl acetate, and polyester resin.
10. The agricultural and horticultural mulch film according to claim 1 wherein a white light reflecting layer having a white light reflecting material dispersed therein is provided inside the agricultural and horticultural mulch film.
11. The agricultural and horticultural covering film according to claim 1,
the agricultural and horticultural covering film has, on one surface thereof: a white light reflecting layer formed by coating a white light reflecting material and an infrared light absorbing layer formed by coating ultrafine particles of an infrared absorbing material on the white light reflecting layer, or,
the agricultural and horticultural covering film has a white light reflecting layer formed by coating a white light reflecting material on one surface thereof and has an infrared light absorbing layer formed by coating ultrafine particles of an infrared absorbing material on the other surface thereof.
12. The agricultural and horticultural covering film according to claim 10 or 11, wherein the white light reflecting material is selected from TiO2、ZrO2、SiO2、Al2O3、MgO、ZnO、CaCO3、BaSO4、ZnS、PbCO3At least one of them.
13. A method for producing an agricultural and horticultural mulch film having an infrared light absorbing layer containing ultrafine particles of an infrared absorbing material,
the infrared absorbing material ultrafine particles are composite tungsten oxide ultrafine particles,
the composite tungsten oxide ultrafine particles are produced so that the ratio of XRD peak intensity of the composite tungsten oxide ultrafine particles becomes 0.13 or more when the XRD peak intensity value on the 220 plane of the silicon powder standard sample 640c produced by NIST is 1,
the composite tungsten oxide ultrafine particles obtained by the production are added to the infrared light absorption layer while maintaining the ratio of the XRD peak top intensities at 0.13 or more.
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